Bridged metal complexes for gas phase polymerizations

ABSTRACT

A gas phase olefin polymerization wherein the catalyst comprises a novel Group 4 transition metal complex containing a boron or aluminum bridging group containing a nitrogen containing group, especially an amido group.

CROSS-REFERENCE TO RELATED APPLICATION

[0001] This application claims benefit of priority from provisionalapplication 60/103511, filed Oct. 8, 1998.

BACKGROUND OF THE INVENTION

[0002] This invention relates to the use of certain bridged Group 4transition metal complexes possessing a unique bridging structure in agas-phase olefin polymerization catalyst. The unique bridge consists ofeither boron or aluminum atoms which are further ligated with nitrogencontaining groups. The unique bridging structures in the complexesprovides for gas-phase olefin polymerization catalysts withexceptionally high catalytic efficiency, and processes giving uniquepolymer properties.

[0003] In Angew. Chem. Int. Ed. Engl., 36, 21, p2338-2340 (1997) and inPhosphorus, Sulfur, and Silicon, 124 & 125, p561-565 (1997) amidosubstituted boron bridged ferrocenophanes useful for formingpoly(ferrocenes) by a ring opening polymerization were disclosed. Thesynthesis and characterization of Group 1 and 2 metal and tin complexesof 1,2-bis(dimethylamino)-1,2-di-9-fluorenyldiboranes were disclosed inChem. Ber., 127, p1901-1908, (1994). Diboranes having structure similarto those employed in the foregoing study were disclosed by the sameresearchers in Eur. J. Inorg. Chem., p505-509 (1998). Ferrocenophanederivatives of similar bisboranes for further molecular property studieswere disclosed by J. Organomet. Chem., 530 p117-120 (1997). InOrganometallics, 16, p4546-4550 (1997) boron bridged ansa metallocenecomplexes including dimethylsulfide and phosphine adducts thereof ofpossible use in Ziegler-Natta-type olefin polymerizations weredisclosed.

[0004] In the patent literature, bridged metal complexes for use asolefin polymerization catalyst components, including such complexescontaining one or more boron atoms in the bridge are genericallydisclosed by EP-A-416,815 and WO 98/39369.

SUMMARY OF THE INVENTION

[0005] The present invention relates to the use of certain bridged Group4 transition metal complexes as olefin polymerization catalysts in agas-phase olefin polymerization, wherein said complexes correspond tothe following formulas:

[0006] wherein:

[0007] M is titanium, zirconium, or hafnium in the +4, +3, or +2oxidation state;

[0008] Y¹ and Y² are independently an anionic, cyclic or non-cyclic,π-bonded group, NR¹, PR¹; NR¹ ₂ or PR¹ ₂;

[0009] Z is boron or aluminum;

[0010] Q is a neutral, anionic or dianionic ligand group depending onthe oxidation state of M;

[0011] j is 1, 2 or 3 depending on the oxidation state of M and theelectronic nature of Q;

[0012] T independently each occurrence is:

[0013] R¹ is independently each occurrence hydrogen, a hydrocarbylgroup, a tri(hydrocarbyl)silyl group, or atri(hydrocarbyl)silylhydrocarbyl group, said R¹ groups containing up to20 atoms not counting hydrogen;

[0014] R⁵ is R¹ or N(R¹)₂; and

[0015] two R¹ groups together or one or more R¹ groups together with R⁵may optionally be joined to form a ring structure.

[0016] It is understood that the foregoing metal complexes may exist asdimers and that one or more Lewis bases may optionally be coordinatedwith the complex or the dimer thereof and that when Y¹ or Y² are theneutral ligands, NR¹ ₂ or PR¹ ₂, the bond to M is a coordinate-covalentbond rather than a covalent bond. In addition, when T is R¹ ₂N and Z isboron, the bond between T and Z, particularly in the compounds offormula 1, may possess double bond characteristics, that is, theresulting group is more accurately depicted by the formula R¹ ₂N═B. Inaddition, suitable catalyst compositions desirably additionally comprisean activating cocatalyst and a support.

DETAILED DESCRIPTION

[0017] The foregoing metal complexes are produced by reaction of ametallated derivative of a compound of one of the formulas:

[0018] wherein Z, T, R¹ and R⁵ are as defined above;

[0019] Y^(1′) and Y^(2′) are an anionic, cyclic or non-cyclic, π-bondedgroup, NR¹, or PR¹; and

[0020] R⁴ is hydrogen or a trimethylsilyl group,

[0021] with a metal salt of the formula MY³ ₄, where M is a Group 4metal, and Y³ is a leaving group, especially halide. The reactants maybe combined either as neat reagents or in an inert solvent. Temperaturesfrom −100° C. to 150° C. are preferred.

[0022] In a particularly preferred embodiment, the complexes of formula1 and formula 2 are prepared in high racemic purity in the +2 formaloxidation state by contacting the metallated derivatives of compounds offormula 1A or formula 2A, with a Group 4 precursor of the formula 3:

[0023] wherein M and Y³ are defined as above,

[0024] R⁶ independently each occurrence is hydrogen, a hydrocarbylgroup, a tri(hydrocarbyl)silyl group, or atri(hydrocarbyl)silylhydrocarbyl group, said R⁶ groups containing up to20 atoms not counting hydrogen; and

[0025] LB is a Lewis base, especially an ether, amine, or phosphine ofup to 20 carbons.

[0026] The complexes are desirably prepared in an inert solvent,especially an aliphatic or aromatic hydrocarbon or ether, employingtemperatures from −100° C. to 150° C. This technique is similar to thatdisclosed in U.S. patent application Ser. No. 265,641, filed Mar. 10,1999, differing in that different starting reagents are employed.

[0027] The process of the present invention can be used in combinationwith one or more additional polymerization processes either in parallelor series, using the same or different reactors.

[0028] Because the catalyst compositions possess improved catalyticefficiencies and improved thermal stability, they are particularlyadapted for use under higher operating temperatures and poor thermaltransport conditions, such as are commonly encountered under gas phasepolymerization conditions.

[0029] All references to the Periodic Table of the Elements herein shallrefer to the Periodic Table of the Elements, published and copyrightedby CRC Press, Inc., 1997. Also, any references to a Group or Groupsshall be to the Groups or Groups reflected in this Periodic Table of theElements using the IUPAC system for numbering groups. Where anyreference is made herein to any publication, patent application orprovisional patent application, the contents thereof are incorporatedherein in its entirety by reference. By the term “π-bonded” as usedherein is meant that bonding occurs through an interaction involvingdelocalized electrons. Finally, by the term, “leaving group” is meant aligand that is readily displaced by another ligand under ligand exchangeconditions.

[0030] The present Group 4 transition metal complexes contain a uniquebridging group: (T-Z) or (T-Z)₂, which imparts improved catalyticproperties when used in combination with one or more activatingcocatalysts or activating techniques in the presence of additionpolymerizable monomers. While not desiring to be bound by theory, it isbelieved that the improvement in catalytic properties for such complexesmay be due to electron donating or electron withdrawing properties ofthe Y¹ and Y² moieties.

[0031] Preferred Group 4 transition metal complexes are those thatcorrespond to formula 1 or 2 are represented in formulas 4, 5, 6, 7, 8and 9:

[0032] wherein M, Z, T, Q and j are as defined above;

[0033] R² is hydrogen, or a hydrocarbyl, halohydrocarbyl,dihydrocarbylamino-hydrocarbyl, tri(hydrocarbylsilyl)hydrocarbyl,Si(R³)₃, N(R³)₂, or OR³ group of up to 20 carbon or silicon atoms, andoptionally two adjacent R² groups can be joined together, therebyforming a fused ring structure, especially an indenyl ligand or asubstituted indenyl ligand; and

[0034] R³ is independently hydrogen, a hydorcarbyl group, atrihydrocarbylsilyl group or a trihydrocarbylsilylhydorcarbyl group,said R³ having up to 20 atoms not counting hydrogen.

[0035] When M is in the +4 oxidation state, j=2 and Q independently eachoccurrence is halide, hydride, hydrocarbyl, silylhydrocarbyl,hydrocarbyloxide, dihydrocarbylamide, said Q having up to 20 atoms notcounting hydrogen. Alternatively, two Q groups may be joined together toform an alkanediyl group or a conjugated C₄₋₄₀ diene ligand which iscoordinated to M in a metallocyclopentene fashion.

[0036] When M is in the +3 oxidation state, j=1 and Q is either 1) amonovalent anionic stabilizing ligand selected from the group consistingof alkyl, cycloalkyl, aryl, silyl, amido, phosphido, alkoxy, aryloxy,sulfido groups, and mixtures thereof, and being further substituted withan amine, phosphine, ether, or thioether containing substituent able toform a coordinate-covalent bond or chelating bond with M said ligandhaving up to 50 atoms not counting hydrogen; or 2) a C₃₋₁₀ hydrocarbylgroup comprising an ethylenic unsaturation able to form an η³ bond withM.

[0037] When M is in the +2 oxidation state, j=1 and Q is a neutralconjugated diene, optionally substituted with one or moretri(hydrocarbyl)silyl or tri(hydrocarbylsilyl)hydrocarbyl groups, said Qhaving up to 40 carbon atoms and forming a π-complex with M.

[0038] Specific examples of the above metal complexes wherein M is inthe +4 oxidation state are shown below in formulas 4a-9a, wherein thedefinitions of M, Z, R¹, R², and R³ are as defined above:

[0039] Specific examples of the above metal complexes wherein M is inthe +4 oxidation state are shown below in formulas 4a-9a, wherein thedefinitions of M, Z, R¹, R², and R³ are as defined above:

[0040] wherein Q, independently each occurrence is a halide,hydrocarbyl, hydrocarbyloxy, or dihydrocarbylamide group of up to 10atoms not counting hydrogen, or two Q groups together form a C₄₋₂₀ dieneligand coordinated to M in a metallocyclopentene fashion. Most highlypreferably Q independently each occurrence is chloride or C₁₋₆hydrocarbyl groups, or two Q groups together form a2-methyl-1,3-butadienyl or 2,3-dimethyl-1,3-butadienyl group.

[0041] Specific examples of the above metal complexes wherein M is inthe +3 oxidation state are shown below in formulas 4b-9b, wherein thedefinitions of M, Z, R¹, R², and R³ are as defined above:

[0042] wherein Q, each occurrence is a monovalent anionic stabilizingligand selected from the group consisting of alkyl, cycloalkyl, aryl,and silyl groups which are further substituted with one or more amine,phosphine, or ether substituents able to form a coordinate-covalent bondor chelating bond with M, said Q having up to 30 non-hydrogen atoms; orQ is a C₃₋₁₀ hydrocarbyl group comprising an ethylenic unsaturation ableto form an 3 bond with M. Most highly preferred examples of such Qligands are 2-N,N-dimethylaminobenzyl, allyl, and 1-methyl-allyl.

[0043] Specific examples of the above metal complexes wherein M is inthe +2 oxidation state are shown below in formulas 4c-9c, wherein thedefinitions of M, Z, R¹, R², and R³ are as defined above:

[0044] wherein Q, each occurrence is a neutral conjugated diene,optionally substituted with one or more tri(hydrocarbyl)silyl groups ortri(hydrocarbyl)silylhydrocarbyl groups, said Q having up to 30 atomsnot counting hydrogen and forming a π-complex with M. Most highlypreferred Q groups are 1,4-diphenyl-1,3-butadiene, 1,3-pentadiene,3-methyl-1,3-pentadiene, 2,4-hexadiene, 1-phenyl-1,3-pentadiene,1,4-dibenzyl-1,3-butadiene, 1,4-ditolyl-1,3-butadiene,1,4-bis(trimethylsilyl)-1,3-butadiene, and 1,4-dinaphthyl-1,3-butadiene.

[0045] Preferably in the foregoing formulas, R¹ independently eachoccurrence is C₁₋₄ alkyl or phenyl, more preferably methyl or isopropyl,most preferably methyl, Y¹ and Y² are both inden-1-yl,2-alkyl-4-arylinden-1-yl, or 3-alkylinden-1-yl, or Y¹ iscyclopentadienyl or alkyl-substituted cyclopentadienyl and Y² isfluorenyl; Z is boron and Q is halide, alkyl, N,N-dialkylamido, or1,4-diphenyl-1,3-butadiene (said alkyl or aryl groups having up to 10carbons). Even more preferably in formulas 4a-c and 8a-c, M is zirconiumor hafnium and R¹ is methyl or isopropyl, most preferably methyl. Duringsynthesis of these complexes, the use of methyl R¹ groups giveselevated, often quantitive, yields of the rac isomer.

[0046] In formulas 5a-c, 6a-c, 8a-c and 9a-c, M is even more preferablytitanium, Z is boron and R¹ is C₁₋₄ alkyl or phenyl, most preferablymethyl or isopropyl.

[0047] Most highly preferred metal complexes are those of formulas 4a-cand 8a-c wherein Y¹ and Y² are both inden-1-yl,2-methyl-4-phenylinden-1-yl, 3-isopropylinden-1-yl, or3-t-butylinden-1-yl groups, especially compositions comprising greaterthan 90 percent rac isomer.

[0048] Specific, but not limiting, metal complexes included with theinvention described in the foregoing formulas are:

[0049] dimethylamidoborane-bis-η⁵-cyclopentadienyl zirconium dichloride;

[0050] dimethylamidoborane-bis-η⁵-cyclopentadienyl zirconium dimethyl;

[0051] dimethylamidoborane-bis-η⁵-cyclopentadienyl zirconiumbis-dimethylamide;

[0052] dimethylamidoborane-bis-η⁵-cyclopentadienyl zirconium2-methyl-1,3-butadiene;

[0053] dimethylamidoborane-bis-η⁵-cyclopentadienyl zirconium2,3-dimethyl-1,3-butadiene;

[0054] dimethylamidoborane-bis-η⁵-cyclopentadienyl zirconium2-N,N-dimethylaminobenzyl;

[0055] dimethylamidoborane-bis-η⁵-cyclopentadienyl zirconium allyl;

[0056] dimethylamidoborane-bis-η⁵-cyclopentadienyl zirconiumη⁴-1,4-diphenyl-1,3-butadiene;

[0057] dimethylamidoborane-bis-η⁵-cyclopentadienyl zirconiumη⁴-2,4-hexadiene;

[0058] dimethylamidoborane-bis-η⁵-cyclopentadienyl zirconiumη⁴-1,4-dinaphthyl-1,3-butadiene;

[0059] dimethylamidoborane-bis-η⁵-cyclopentadienyl zirconiumη⁴-1-phenyl-1,3-pentadiene;

[0060] dimethylamidoborane-bis-η⁵-cyclopentadienyl zirconiumη⁵-1,3-pentadiene;

[0061] dimethylamidoborane-bis-η⁵-n-butylcyclopentadienyl zirconiumdichloride;

[0062] dimethylamidoborane-bis-η⁵-n-butylcyclopentadienyl zirconiumdimethyl;

[0063] dimethylamidoborane-bis-η⁵-n-butylcyclopentadienyl zirconiumbis-dimethylamide;

[0064] dimethylamidoborane-bis-η⁵-n-butylcyclopentadienylzirconium2-methyl-1,3-butadiene;

[0065] dimethylamidoborane-bis-η⁵-n-butylcyclopentadienyl zirconium2,3-dimethyl-1,3-butadiene;

[0066] dimethylamidoborane-bis-η⁵-n-butylcyclopentadienyl zirconium2-N,N-dimethylaminobenzyl;

[0067] dimethylamidoborane-bis-η⁵-n-butylcyclopentadienyl zirconiumallyl;

[0068] dimethylamidoborane-bis-η⁵-n-butylcyclopentadienyl zirconiumη⁴-1,4-diphenyl-1,3-butadiene;

[0069] dimethylamidoborane-bis-η⁵-n-butylcyclopentadienyl zirconiumη⁴-2,4-hexadiene;

[0070] dimethylamidoborane-bis-η⁵-n-butylcyclopentadienyl zirconiumη⁴-1,4-dinaphthyl-1,3-butadiene;

[0071] dimethylamidoborane-bis-η⁵-n-butylcyclopentadienyl zirconiumη⁴-1-phenyl-1,3-pentadiene;

[0072] dimethylamidoborane-bis-η⁵-n-butylcyclopentadienyl zirconium η⁵-1,3-pentadiene;

[0073] dimethylamidoborane-bis-η⁵-inden-1-ylzirconium dichloride;

[0074] dimethylamidoborane-bis-η⁵-inden-1-ylzirconium dimethyl;

[0075] dimethylamidoborane-bis-η⁵-inden-1-ylzirconium bis-dimethylamide;

[0076] dimethylamidoborane-bis-η⁵-inden-1-ylzirconium2-methyl-1,3-butadiene;

[0077] dimethylamidoborane-bis-η⁵-inden-1-ylzirconium2,3-dimethyl-1,3-butadiene;

[0078] dimethylamidoborane-bis-η⁵-inden-1-ylzirconium2-N,N-dimethylaminobenzyl;

[0079] dimethylamidoborane-bis-η⁵-inden-1-ylzirconium allyl;

[0080] dimethylamidoborane-bis-η⁵-inden-1-ylzirconiumη⁴-1,4-diphenyl-1,3-butadiene;

[0081] dimethylamidoborane-bis-η⁵-inden-1-ylzirconium η⁴-2,4-hexadiene;

[0082] dimethylamidoborane-bis-η⁵-inden-1-ylzirconiumη⁴-1,4-dinaphthyl-1,3-butadiene;

[0083] dimethylamidoborane-bis-η⁵-inden-1-ylzirconiumη⁴-1-phenyl-1,3-pentadiene;

[0084] dimethylamidoborane-bis-η⁵-inden-1-ylzirconium η⁴-1,3-pentadiene;

[0085] dimethylamidoborane-bis-η⁵-(2-methylinden-1-yl)zirconiumdichloride;

[0086] dimethylamidoborane-bis-η⁵-(2-methylinden-1-yl)zirconiumdimethyl;

[0087] dimethylamidoborane-bis-η⁵-(2-methylinden-1-yl)zirconiumbis-dimethylamide;

[0088] dimethylamidoborane-bis-η⁵-(2-methylinden-1-yl)zirconium2-methyl-1,3-butadiene;

[0089] dimethylamidoborane-bis-η⁵-(2-methylinden-1-yl)zirconium2,3-dimethyl-1,3-butadiene;

[0090] dimethylamidoborane-bis-η⁵-(2-methylinden-1-yl)zirconium2-N,N-dimethylaminobenzyl;

[0091] dimethylamidoborane-bis-η⁵-(2-methylinden-1-yl)zirconium allyl;

[0092] dimethylamidoborane-bis-η⁵-(2-methylinden-1-yl)zirconiumη⁴-1,4-diphenyl-1,3-butadiene;

[0093] dimethylamidoborane-bis-η⁵-(2-methylinden-1-yl)zirconiumη⁴-2,4-hexadiene;

[0094] dimethylamidoborane-bis-η⁵-(2-methylinden-1-yl)zirconiumη⁴-1,4-dinaphthyl-1,3-butadiene;

[0095] dimethylamidoborane-bis-η⁵-(2-methylinden-1-yl)zirconiumη⁴-1-phenyl-1,3-pentadiene;

[0096] dimethylamidoborane-bis-η⁵-(2-methylinden-1-yl)zirconiumη⁴-1,3-pentadiene;

[0097] dimethylamidoborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconiumdichloride;

[0098] dimethylamidoborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconiumdimethyl;

[0099] dimethylamidoborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconiumbis-dimethylamide;

[0100] dimethylamidoborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconium2-methyl-1,3-butadiene;

[0101] dimethylamidoborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconium2,3-dimethyl-1,3-butadiene;

[0102] dimethylamidoborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconium2-N,N-dimethylaminobenzyl;

[0103] dimethylamidoborane-bis-η⁵(2- methyl-4-phenylinden-1-yl)zirconiumallyl;

[0104] dimethylamidoborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconiumη⁴-1,4-diphenyl-1,3-butadiene;

[0105] dimethylamidoborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconiumη⁴-2,4-hexadiene;

[0106] dimethylamidoborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconiumη⁴-1,4-dinaphthyl-1,3-butadiene;

[0107] dimethylamidoborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconiumη⁴-1-phenyl-1,3-pentadiene;

[0108] dimethylamidoborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconiumη⁴-1,3-pentadiene;

[0109] dimethylamidoborane-bis-η⁵-(2-ethyl-4-phenylinden-1-yl)zirconiumdichloride;

[0110] dimethylamidoborane-bis-η⁵-(2-ethyl-4-phenylinden-1-yl)zirconiumdimethyl;

[0111] dimethylamidoborane-bis-η⁵-(2-ethyl-4-phenylinden-1-yl)zirconiumbis-dimethylamide;

[0112] dimethylamidoborane-bis-η⁵-(2-ethyl-4-phenylinden-1-yl)zirconium2-methyl-1,3-butadiene;

[0113] dimethylamidoborane-bis-η⁵-(2-ethyl-4-phenylinden-1-yl)zirconium2,3-dimethyl-1,3-butadiene;

[0114] dimethylamidoborane-bis-η⁵-(2-ethyl-4-phenylinden-1-yl)zirconium2-N,N-dimethylaminobenzyl;

[0115] dimethylamidoborane-bis-η⁵-(2-ethyl-4-phenylinden-1-yl)zirconiumallyl;

[0116] dimethylamidoborane-bis-η⁵-(2-ethyl-4-phenylinden-1-yl)zirconiumη⁴-1,4-diphenyl-1,3-butadiene;

[0117] dimethylamidoborane-bis-η⁵-(2-ethyl-4-phenylinden-1-yl)zirconiumη⁴-2,4-hexadiene;

[0118] dimethylamidoborane-bis-η⁵-(2-ethyl-4-phenylinden-1-yl)zirconiumη⁴-1,4-dinaphthyl-1,3-butadiene;

[0119] dimethylamidoborane-bis-η⁵(2-ethyl-4-phenylinden-1-yl)zirconiumη⁴-1-phenyl-1,3-pentadiene;

[0120] dimethylamidoborane-bis-η⁵-(2-ethyl-4-phenylinden-1-yl)zirconiumη⁴-1,3-pentadiene;

[0121]dimethylamidoborane-bis-η⁵-(2-isopropyl-4-phenylinden-1-yl)zirconiumdichloride;

[0122]dimethylamidoborane-bis-η⁵-(2-isopropyl-4-phenylinden-1-yl)zirconiumdimethyl;

[0123]dimethylamidoborane-bis-η⁵-(2-isopropyl-4-phenylinden-1-yl)zirconiumbis-dimethylamide;

[0124]dimethylamidoborane-bis-η⁵-(2-isopropyl-4-phenylinden-1-yl)zirconium2-methyl-1,3-butadiene;

[0125]dimethylamidoborane-bis-η⁵-(2-isopropyl-4-phenylinden-1-yl)zirconium2,3-dimethyl-1,3-butadiene;

[0126]dimethylamidoborane-bis-η⁵-(2-isopropyl-4-phenylinden-1-yl)zirconium2-N,N-dimethylaminobenzyl;

[0127]dimethylamidoborane-bis-η⁵-(2-isopropyl-4-phenylinden-1-yl)zirconiumallyl;

[0128]dimethylamidoborane-bis-η⁵-(2-isopropyl-4-phenylinden-1-yl)zirconiumη⁴-1,4-diphenyl-1,3-butadiene;

[0129]dimethylamidoborane-bis-η⁵-(2-isopropyl-4-phenylinden-1-yl)zirconiumη⁴-2,4-hexadiene;

[0130]dimethylamidoborane-bis-η⁵-(2-isopropyl-4-phenylinden-1-yl)zirconiumη⁴-1,4-dinaphthyl-1,3-butadiene;

[0131]dimethylamidoborane-bis-η⁵-(2-isopropyl-4-phenylinden-1-yl)zirconiumη⁴-1-phenyl-1,3-pentadiene;

[0132]dimethylamidoborane-bis-η⁵-(2-isopropyl-4-phenylinden-1-yl)zirconiumη⁴-1,3-pentadiene;

[0133]dimethylamidoborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)zirconiumdichloride;

[0134]dimethylamidoborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)zirconiumdimethyl;

[0135]dimethylamidoborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)zirconiumbis-dimethylamide;

[0136]dimethylamidoborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)zirconium2-methyl-1,3-butadiene;

[0137]dimethylamidoborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)zirconium2,3-dimethyl-1,3-butadiene;

[0138]dimethylamidoborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)zirconium2-N,N-dimethylaminobenzyl;

[0139]dimethylamidoborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)zirconiumallyl;

[0140]dimethylamidoborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)zirconiumη⁴-1,4-diphenyl-1,3-butadiene;

[0141]dimethylamidoborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)zirconiumη⁴-2,4-hexadiene;

[0142]dimethylamidoborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)zirconiumη⁴-1,4-dinaphthyl-1,3-butadiene;

[0143]dimethylamidoborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)zirconiumη⁴-1-phenyl-1,3-pentadiene;

[0144]dimethylamidoborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)zirconiumη⁴-1,3-pentadiene;

[0145]dimethylamidoborane-bis-η⁵-(2-methyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconiumdichloride;

[0146]dimethylamidoborane-bis-η⁵-(2-methyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconiumdimethyl;

[0147]dimethylamidoborane-bis-η⁵-(2-methyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconiumbis-dimethylamide;

[0148]dimethylamidoborane-bis-η⁵-(2-methyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium2-methyl-1,3-butadiene;

[0149]dimethylamidoborane-bis-η⁵-(2-methyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium2,3-dimethyl-1,3-butadiene;

[0150]dimethylamidoborane-bis-η⁵-(2-methyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium2-N,N-dimethylaminobenzyl;

[0151]dimethylamidoborane-bis-η⁵-(2-methyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconiumallyl;

[0152]dimethylamidoborane-bis-η⁵-(2-methyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconiumη²-1,4-diphenyl-1,3-butadiene;

[0153]dimethylamidoborane-bis-η⁵-(2-methyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconiumη⁴-2,4-hexadiene;

[0154]dimethylamidoborane-bis-η⁵-(2-methyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconiumη⁴-1,4-dinaphthyl-1,3-butadiene;

[0155]dimethylamidoborane-bis-η⁵-(2-methyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconiumη⁴-1-phenyl-1,3-pentadiene;

[0156]dimethylamidoborane-bis-η⁵-(2-methyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconiumη⁴-1,3-pentadiene;

[0157]dimethylamidoborane-bis-η⁵-(2-ethyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconiumdichloride;

[0158]dimethylamidoborane-bis-η⁵-(2-ethyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconiumdimethyl;

[0159]dimethylamidoborane-bis-η⁵-(2-ethyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconiumbis-dimethylamide;

[0160]dimethylamidoborane-bis-η⁵-(2-ethyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium2-methyl-1,3-butadiene;

[0161]dimethylamidoborane-bis-η⁵-(2-ethyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium2,3-dimethyl-1,3-butadiene;

[0162]dimethylamidoborane-bis-η⁵-(2-ethyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium2-N,N-dimethylaminobenzyl;

[0163]dimethylamidoborane-bis-η⁵-(2-ethyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconiumallyl;

[0164]dimethylamidoborane-bis-η⁵-(2-ethyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconiumη⁴-1,4-diphenyl-1,3-butadiene;

[0165]dimethylamidoborane-bis-η⁵-(2-ethyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconiumη⁴-2,4-hexadiene;

[0166]dimethylamidoborane-bis-η⁵-(2-ethyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconiumη⁴-1,4-dinaphthyl-1,3-butadiene;

[0167]dimethylamidoborane-bis-η⁵-(2-ethyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconiumη⁴-1-phenyl-1,3-pentadiene;

[0168]dimethylamidoborane-bis-η⁵-(2-ethyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconiumη⁴-1,3-pentadiene;

[0169]dimethylamidoborane-bis-η⁵-(2-isopropyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconiumdichloride;

[0170]dimethylamidoborane-bis-η⁵-(2-isopropyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconiumdimethyl;

[0171]dimethylamidoborane-bis-η⁵-(2-isopropyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconiumbis-dimethylamide;

[0172]dimethylamidoborane-bis-η⁵-(2-isopropyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium2-methyl-1,3-butadiene;

[0173]dimethylamidoborane-bis-η⁵-(2-isopropyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium2,3-dimethyl-1,3-butadiene;

[0174]dimethylamidoborane-bis-η⁵-(2-isopropyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium2-N,N-dimethylaminobenzyl;

[0175]dimethylamidoborane-bis-η⁵-(2-isopropyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconiumallyl;

[0176]dimethylamidoborane-bis-η⁵-(2-isopropyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconiumη⁴-1,4-diphenyl-1,3-butadiene;

[0177]dimethylamidoborane-bis-η⁵-(2-isopropyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconiumη⁴-2,4-hexadiene;

[0178]dimethylamidoborane-bis-η⁵-(2-isopropyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconiumη⁴-1,4-dinaphthyl-1,3-butadiene;

[0179]dimethylamidoborane-bis-η⁵-(2-isopropyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconiumη⁴-1-phenyl-1,3-pentadiene;

[0180]dimethylamidoborane-bis-η⁵-(2-isopropyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconiumη⁴-1,3-pentadiene;

[0181] dimethylamidoborane-bis-η⁵-(3-isopropylinden-1-yl)zirconiumdichloride;

[0182] dimethylamidoborane-bis-η⁵-(3-isopropylinden-1-yl)zirconiumdimethyl;

[0183] dimethylamidoborane-bis-η⁵-(3-isopropylinden-1-yl)zirconiumbis-dimethylamide;

[0184] dimethylamidoborane-bis-η⁵-(3-isopropylinden-1-yl)zirconium2-methyl-1,3-butadiene;

[0185] dimethylamidoborane-bis-η⁵-(3-isopropylinden-1-yl)zirconium2,3-dimethyl-1,3-butadiene;

[0186] dimethylamidoborane-bis-η⁵-(3-isopropylinden-1-yl)zirconium2-N,N-dimethylaminobenzyl;

[0187] dimethylamidoborane-bis-η⁵-(3-isopropylinden-1-yl)zirconiumallyl;

[0188] dimethylamidoborane-bis-η⁵-(3-isopropylinden-1-yl)zirconiumη⁴-1,4-diphenyl-1,3-butadiene;

[0189] dimethylamidoborane-bis-η⁵-(3-isopropylinden-1-yl)zirconiumη⁴-2,4-hexadiene;

[0190] dimethylamidoborane-bis-η⁵-(3-isopropylinden-1-yl)zirconiumη⁴-1,4-dinaphthyl-1,3-butadiene;

[0191] dimethylamidoborane-bis-η⁵-(3-isopropylinden-1-yl)zirconiumη⁴-1-phenyl-1,3-pentadiene;

[0192] dimethylamidoborane-bis-η⁵-(3-isopropylinden-1-yl)zirconiumη⁴-1,3-pentadiene;

[0193] dimethylamidoborane-bis-η⁵-(3-t-butylinden-1-yl)zirconiumdichloride;

[0194] dimethylamidoborane-bis-η⁵-(3-t-butylinden-1-yl)zirconiumdimethyl;

[0195] dimethylamidoborane-bis-η⁵-(3-t-butylinden-1-yl)zirconiumbis-dimethylamide;

[0196] dimethylamidoborane-bis-η⁵-(3-t-butylinden-1-yl)zirconium2-methyl-1,3-butadiene;

[0197] dimethylamidoborane-bis-η⁵-(3-t-butylinden-1-yl)zirconium2,3-dimethyl-1,3-butadiene;

[0198] dimethylamidoborane-bis-η⁵-(3-t-butylinden-1-yl)zirconium2-N,N-dimethylaminobenzyl;

[0199] dimethylamidoborane-bis-η⁵-(3-t-butylinden-1-yl)zirconium allyl;

[0200] dimethylamidoborane-bis-η⁵-(3-t-butylinden-1-yl)zirconiumη⁴-1,4-diphenyl-1,3-butadiene;

[0201] dimethylamidoborane-bis-η⁵-(3-t-butylinden-1-yl)zirconiumη⁴-2,4-hexadiene;

[0202] dimethylamidoborane-bis-η⁵-(3-t-butylinden-1-yl)zirconiumη⁴-1,4-dinaphthyl-1,3-butadiene;

[0203] dimethylamidoborane-bis-η⁵-(3-t-butylinden-1-yl)zirconiumη⁴-1-phenyl-1,3-pentadiene;

[0204] dimethylamidoborane-bis-η⁵-(3-t-butylinden-1-yl)zirconiumη⁴-1,3-pentadiene;

[0205] diisopropylamidoborane-bis-η⁵-cyclopentadienylzirconiumdichloride;

[0206] diisopropylamidoborane-bis-η⁵-cyclopentadienylzirconium dimethyl;

[0207] diisopropylamidoborane-bis-η⁵-cyclopentadienylzirconiumbis-dimethylamide;

[0208] diisopropylamidoborane-bis-η⁵-cyclopentadienylzirconium2-methyl-1,3-butadiene;

[0209] diisopropylamidoborane-bis-η⁵-cyclopentadienylzirconium2,3-dimethyl-1,3-butadiene;

[0210] diisopropylamidoborane-bis-η⁵-cyclopentadienylzirconium2-N,N-dimethylaminobenzyl;

[0211] diisopropylamidoborane-bis-η⁵-cyclopentadienylzirconium allyl;

[0212] diisopropylamidoborane-bis-η⁵-cyclopentadienylzirconiumη⁴-1,4-diphenyl-1,3-butadiene;

[0213] diisopropylamidoborane-bis-η⁵-cyclopentadienylzirconiumη⁴-2,4-hexadiene;

[0214] diisopropylamidoborane-bis-η⁵-cyclopentadienylzirconiumη⁴-1,4-dinaphthyl-1,3-butadiene;

[0215] diisopropylamidoborane-bis-η⁵-cyclopentadienylzirconiumη⁴-1-phenyl-1,3-pentadiene;

[0216] diisopropylamidoborane-bis-η⁵-cyclopentadienylzirconiumη⁴-1,3-pentadiene;

[0217] diisopropylamidoborane-bis-η⁵-inden-1-ylzirconium dichloride;

[0218] diisopropylamidoborane-bis-η⁵-inden-1-ylzirconium dimethyl;

[0219] diisopropylamidoborane-bis-η⁵-inden-1-ylzirconiumbis-dimethylamide;

[0220] diisopropylamidoborane-bis-η⁵-inden-1-ylzirconium2-methyl-1,3-butadiene;

[0221] diisopropylamidoborane-bis-η⁵-inden-1-ylzirconium2,3-dimethyl-1,3-butadiene;

[0222] diisopropylamidoborane-bis-η⁵-inden-1-ylzirconium2-N,N-dimethylaminobenzyl;

[0223] diisopropylamidoborane-bis-η⁵-inden-1-ylzirconium allyl;

[0224] diisopropylamidoborane-bis-η⁵-inden-1-ylzirconiumη⁴-1,4-diphenyl-1,3-butadiene;

[0225] diisopropylamidoborane-bis-η⁵-inden-1-ylzirconiumη⁴-2,4-hexadiene;

[0226] diisopropylamidoborane-bis-η⁵-inden-1-ylzirconiumη⁴-1,4-dinaphthyl-1,3-butadiene;

[0227] diisopropylamidoborane-bis-η⁵-inden-1-ylzirconiumη⁴-1-phenyl-1,3-pentadiene;

[0228] diisopropylamidoborane-bis-η⁵-inden-1-ylzirconiumη⁴-1,3-pentadiene;

[0229] diisopropylamidoborane-bis-η⁵-(2-methylinden-1-yl)zirconiumdichloride;

[0230] diisopropylamidoborane-bis-η⁵-(2-methylinden-1-yl)zirconiumdimethyl;

[0231] diisopropylamidoborane-bis-η⁵-(2-methylinden-1-yl)zirconiumbis-dimethylamide;

[0232] diisopropylamidoborane-bis-η⁵-(2-methylinden-1-yl)zirconium2-methyl-1,3-butadiene;

[0233] diisopropylamidoborane-bis-η⁵-(2-methylinden-1-yl)zirconium2,3-dimethyl-1,3-butadiene;

[0234] diisopropylamidoborane-bis-η⁵-(2-methylinden-1-yl)zirconium2-N,N-dimethylaminobenzyl;

[0235] diisopropylamidoborane-bis-η⁵-(2-methylinden-1-yl)zirconiumallyl;

[0236] diisopropylamidoborane-bis-η⁵-(2-methylinden-1-yl)zirconiumη⁴-1,4-diphenyl-1,3-butadiene;

[0237] diisopropylamidoborane-bis-η⁵-(2-methylinden-1-yl)zirconiumη⁴-2,4-hexadiene;

[0238] diisopropylamidoborane-bis-η⁵-(2-methylinden-1-yl)zirconiumη⁴-1,4-dinaphthyl-1,3-butadiene;

[0239] diisopropylamidoborane-bis-η⁵-(2-methylinden-1-yl)zirconiumη⁴-1-phenyl-1,3-pentadiene;

[0240] diisopropylamidoborane-bis-η⁵-(2-methylinden-1-yl)zirconiumη⁴-1,3-pentadiene;

[0241]diisopropylamidoborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconiumdichloride;

[0242]diisopropylamidoborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconiumdimethyl;

[0243]diisopropylamidoborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconiumbis-dimethylamide;

[0244]diisopropylamidoborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconium2-methyl-1,3-butadiene;

[0245]diisopropylamidoborane-bis-η⁵(2-methyl-4-phenylinden-1-yl)zirconium2,3-dimethyl-1,3-butadiene;

[0246]diisopropylamidoborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconium2-N,N-dimethylaminobenzyl;

[0247]diisopropylamidoborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconium-allyl;

[0248]diisopropylamidoborane-bis-η⁵(2-methyl-4-phenylinden-1-yl)zirconiumη⁴-1,4-diphenyl-1,3-butadiene;

[0249]diisopropylamidoborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconiumη⁴-2,4-hexadiene;

[0250]diisopropylamidoborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconiumη⁴-1,4-dinaphthyl-1,3-butadiene;

[0251]diisopropylamidoborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconiumη⁴-1-phenyl-1,3-pentadiene;

[0252]diisopropylamidoborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconiumη⁴-1,3-pentadiene;

[0253]diisopropylamidoborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)zirconiumdichloride;

[0254]diisopropylamidoborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)zirconiumdimethyl;

[0255]diisopropylamidoborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)zirconiumbis-dimethylamide;

[0256]diisopropylamidoborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)zirconium2-methyl-1,3-butadiene;

[0257]diisopropylamidoborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)zirconium2,3-dimethyl-1,3-butadiene;

[0258]diisopropylamidoborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)zirconium2-N,N-dimethylaminobenzyl;

[0259]diisopropylamidoborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)zirconiumallyl;

[0260]diisopropylamidoborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)zirconiumη⁴-1,4-diphenyl-1,3-butadiene;

[0261]diisopropylamidoborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)zirconiumη⁴-2,4-hexadiene;

[0262]diisopropylamidoborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)zirconiumη⁴-1,4-dinaphthyl-1,3-butadiene;

[0263]diisopropylamidoborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)zirconiumη⁴-1-phenyl-1,3-pentadiene;

[0264]diisopropylamidoborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)zirconiumη⁴-1,3-pentadiene;

[0265]diisopropylamidoborane-bis-η⁵-(2-methyl-4-(3,5-dimethylphenyl)inden-1-yl)zirconiumdichloride;

[0266]diisopropylamidoborane-bis-η⁵-(2-methyl-(3,5-diethylphenyl)inden-1-yl)zirconiumdimethyl;

[0267]diisopropylamidoborane-bis-η⁵-(2-methyl-4-(3,5-dimethylphenyl)inden-1-yl)zirconiumbis-dimethylamide;

[0268]diisopropylamidoborane-bis-η⁵-(2-methyl-4-(3,5-dimethylphenyl)inden-1-yl)zirconium2-methyl-1,3-butadiene;

[0269]diisopropylamidoborane-bis-η⁵-(2-methyl-4-(3,5-dimethylphenyl)inden-1-yl)zirconium2,3-dimethyl-1,3-butadiene;

[0270]diisopropylamidoborane-bis-η⁵-(2-methyl-4-(3,5-dimethylphenyl)inden-1-yl)zirconium2-N,N-dimethylaminobenzyl;

[0271]diisopropylamidoborane-bis-η⁵-(2-methyl-4-(3,5-dimethylphenyl)inden-1-yl)zirconiumallyl;

[0272]diisopropylamidoborane-bis-η⁵-(2-methyl-4-(3,5-dimethylphenyl)inden-1-yl)zirconiumη⁴-1,4-diphenyl-1,3-butadiene;

[0273]diisopropylamidoborane-bis-η⁵-(2-methyl-4-(3,5-dimethylphenyl)inden-1-yl)zirconiumη⁴-2,4-hexadiene;

[0274]diisopropylamidoborane-bis-η⁵-(2-methyl-4-(3,5-dimethylphenyl)inden-1-yl)zirconiumη⁴-1,4-dinaphthyl-1,3-butadiene;

[0275]diisopropylamidoborane-bis-η⁵-(2-methyl-4-(3,5-dimethylphenyl)inden-1-yl)zirconiumη⁴-1-phenyl-1,3-pentadiene;

[0276]diisopropylamidoborane-bis-η⁵-(2-methyl-4-(3,5-dimethylphenyl)inden-1-yl)zirconiumη⁴-1,3-pentadiene;

[0277]diisopropylamidoborane-bis-η⁵-(2-methyl-4-(3,5-difluoromethylphenyl)inden-1-yl)zirconiumdichloride;

[0278]diisopropylamidoborane-bis-η⁵-(2-methyl-4-(3,5-difluoromethylphenyl)inden-1-yl)zirconiumdimethyl;

[0279]diisopropylamidoborane-bis-η⁵-(2-methyl-4-(3,5-difluoromethylphenyl)inden-1-yl)zirconiumbis-dimethylamide;

[0280]diisopropylamidoborane-bis-η⁵-(2-methyl-4-(3,5-difluoromethylphenylinden-1-yl)zirconium 2-methyl-1,3-butadiene;

[0281]diisopropylamidoborane-bis-η⁵-(2-methyl-4-(3,5-difluoromethylphenyl)inden-1-yl)zirconium2,3-dimethyl-1,3-butadiene;

[0282]diisopropylamidoborane-bis-η⁵-(2-methyl-4-(3,5-difluoromethylphenyl)inden-1-yl)zirconium2-N,N-dimethylaminobenzyl;

[0283]diisopropylamidoborane-bis-η⁵-(2-methyl-4-(3,5-difluoromethylphenyl)inden-1-yl)zirconiumallyl;

[0284]diisopropylamidoborane-bis-η⁵-(2-methyl-4-(3,5-difluoromethylphenyl)inden-1-yl)zirconiumη^(1,4)-diphenyl-1,3-butadiene;

[0285]diisopropylamidoborane-bis-η⁵-(2-methyl-4-(3,5-difluoromethylphenyl)inden-1-yl)zirconiumη⁴-2,4-hexadiene;

[0286]diisopropylamidoborane-bis-η⁵-(2-methyl-4-(3,5-difluoromethylphenyl)inden-1-yl)zirconiumη⁴-1,4-dinaphthyl-1,3-butadiene;

[0287]diisopropylamidoborane-bis-η⁵-(2-methyl-4-(3,5-difluoromethylphenyl)inden-1-yl)zirconiumη⁴-1-phenyl-1,3-pentadiene;

[0288]diisopropylamidoborane-bis-η⁵-(2-methyl-4-(3,5-difluoromethylphenyl)inden-1-yl)zirconiumη⁴-1,3-pentadiene;

[0289]diisopropylamidoborane-bis-η⁵-(2-ethyl-4-phenylinden-1-yl)zirconiumdichloride;

[0290]diisopropylamidoborane-bis-η⁵-(2-ethyl-4-phenylinden1-yl)zirconiumdimethyl;

[0291]diisopropylamidoborane-bis-η⁵-(2-ethyl-4-phenylinden-1-yl)zirconiumbis-dimethylamide;

[0292]diisopropylamidoborane-bis-η⁵-(2-ethyl-4-phenylinden-1-yl)zirconium2-methyl-1,3-butadiene;

[0293]diisopropylamidoborane-bis-η⁵-(2-ethyl-4-phenylinden1-yl)zirconium2,3-dimethyl-1,3-butadiene;

[0294]diisopropylamidoborane-bis-η⁵-(2-ethyl-4-phenylinden-1-yl)zirconium2-N,N-dimethylaminobenzyl;

[0295]diisopropylamidoborane-bis-η⁵-(2-ethyl-4-phenylinden-1-yl)zirconiumallyl;

[0296]diisopropylamidoborane-bis-η⁵-(2-ethyl-4-phenylinden-1-yl)zirconiumη⁴-1,4-diphenyl-1,3-butadiene;

[0297]diisopropylamidoborane-bis-η⁵-(2-ethyl-4-phenylinden-1-yl)zirconiumη⁴-2,4-hexadiene;

[0298]diisopropylamidoborane-bis-η⁵-(2-ethyl-4-phenylinden-1-yl)zirconiumη⁴-1,4-dinaphthyl-1,3-butadiene;

[0299]diisopropylamidoborane-bis-η⁵-(2-ethyl-4-phenylinden-1-yl)zirconiumη⁴-1-phenyl-1,3-pentadiene;

[0300]diisopropylamidoborane-bis-η⁵-(2-ethyl-47phenylinden-1-yl)zirconium1-1,3-pentadiene;

[0301]diisopropylamidoborane-bis-η⁵-(2-isopropyl-4-phenylinden-1-yl)zirconiumdichloride;

[0302]diisopropylamidoborane-bis-η⁵-(2-isopropyl-4-phenylinden-1-yl)zirconiumdimethyl;

[0303]diisopropylamidoborane-bis-η⁵-(2-isopropyl-4-phenylinden-1-yl)zirconiumbis-dimethylamide;

[0304]diisopropylamidoborane-bis-η⁵-(2-isopropyl-4-phenylinden-1-yl)zirconium2-methyl-1,3-butadiene;

[0305]diisopropylamidoborane-bis-η⁵-(2-isopropyl-4-phenylinden-1-yl)zirconium2,3-dimethyl-1,3-butadiene;

[0306]diisopropylamidoborane-bis-η⁵-(2-isopropyl-4-phenylinden-1-yl)zirconium2-N,N-dimethylaminobenzyl;

[0307]diisopropylamidoborane-bis-η⁵-(2-isopropyl-4-phenylinden-1-yl)zirconiumallyl;

[0308]diisopropylamidoborane-bis-η⁵-(2-isopropyl-4-phenylinden-1-yl)zirconiumη⁴-1,4-diphenyl-1,3-butadiene;

[0309]diisopropylamidoborane-bis-η⁵-(2-isopropyl-4-phenylinden-1-yl)zirconiumη⁴-2,4-hexadiene;

[0310]diisopropylamidoborane-bis-η⁵-(2-isopropyl-4-phenylinden-1-yl)zirconiumη⁴-1,4-dinaphthyl-1,3-butadiene;

[0311]diisopropylamidoborane-bis-η⁵-(2-isopropyl-4-phenylinden-1-yl)zirconiumη⁴-1-phenyl-1,3-pentadiene;

[0312]diisopropylamidoborane-bis-η⁵-(2-isopropyl-4-phenylinden-1-yl)zirconiumη⁴-1,3-pentadiene;

[0313] diisopropylamidoborane-bis-η⁵-(3-isopropylinden-1-yl)zirconiumdichloride;

[0314] diisopropylamidoborane-bis-η⁵-(3-isopropylinden-1-yl)zirconiumdimethyl;

[0315] diisopropylamidoborane-bis-η⁵-(3-isopropylinden-1-yl)zirconiumbis-dimethylamide;

[0316] diisopropylamidoborane-bis-η⁵-(3-isopropylinden-1-yl)zirconium2-methyl-1,3-butadiene;

[0317] diisopropylamidoborane-bis-η⁵-(3-isopropylinden-1-yl)zirconium2,3-dimethyl-1,3-butadiene;

[0318] diisopropylamidoborane-bis-η⁵-(3-isopropylinden-1-yl)zirconium2-N,N-dimethylaminobenzyl;

[0319] diisopropylamidoborane-bis-η⁵-(3-isopropylinden-1-yl)zirconiumallyl;

[0320] diisopropylamidoborane-bis-η⁵-(3-isopropylinden-1-yl)zirconiumη⁴-1,4-diphenyl-1,3-butadiene;

[0321] diisopropylamidoborane-bis-η⁵-(3-isopropylinden-1-yl)zirconiumη⁴-2,4-hexadiene;

[0322] diisopropylamidoborane-bis-η⁵-(3-isopropylinden-1-yl)zirconiumη⁴-1,4-dinaphthyl-1,3-butadiene;

[0323] diisopropylamidoborane-bis-η⁵-(3-isopropylinden-1-yl)zirconiumη⁴-1-phenyl-1,3-pentadiene;

[0324] diisopropylamidoborane-bis-η⁵-(3-isopropylinden-1-yl)zirconiumη⁴-1,3-pentadiene;

[0325] diisopropylamidoborane-bis-η⁵-(3-t-butylinden-1-yl)zirconiumdichloride;

[0326] diisopropylamidoborane-bis-η⁵-(3-t-butylinden-1-yl)zirconiumdimethyl;

[0327] diisopropylamidoborane-bis-η⁵-(3-t-butylinden-1-yl)zirconiumbis-dimethylamide;

[0328] diisopropylamidoborane-bis-η⁵-(3-t-butylinden-1-yl)zirconium2-methyl-1,3-butadiene;

[0329] diisopropylamidoborane-bis-η⁵-(3-t-butylinden-1-yl)zirconium2,3-dimethyl-1,3-butadiene;

[0330] diisopropylamidoborane-bis-η⁵-(3-t-butylinden-1-yl)zirconium2-N,N-dimethylaminobenzyl;

[0331] diisopropylamidoborane-bis-η⁵-(3-t-butylinden-1-yl)zirconiumallyl;

[0332] diisopropylamidoborane-bis-η⁵-(3-t-butylinden-1-yl)zirconiumη⁴-1,4-diphenyl-1,3-butadiene;

[0333] diisopropylamidoborane-bis-η⁵-(3-t-butylinden-1-yl)zirconiumη⁴-2,4-hexadiene;

[0334] diisopropylamidoborane-bis-η⁵-(3-t-butylinden-1-yl)zirconiumη⁴-1,4-dinaphthyl-1,3-butadiene;

[0335] diisopropylamidoborane-bis-η⁵-(3-t-butylinden-1-yl)zirconiumη⁴-phenyl-1,3-pentadiene;

[0336] diisopropylamidoborane-bis-η⁵-(3-t-butylinden-1-yl)zirconiumη⁴-1,3-pentadiene;

[0337] diphenylamidoborane-bis-η⁵-cyclopentadienyl zirconium dichloride;

[0338] diphenylamidoborane-bis-η⁵-cyclopentadienyl zirconium dimethyl;

[0339] diphenylamidoborane-bis-η⁵-cyclopentadienyl zirconiumbis-dimethylamide;

[0340] diphenylamidoborane-bis-η⁵-cyclopentadienyl zirconium2-methyl-1,3-butadiene;

[0341] diphenylamidoborane-bis-η⁵-cyclopentadienyl zirconium2,3-dimethyl-1,3-butadiene;

[0342] diphenylamidoborane-bis-η⁵-cyclopentadienyl zirconium2-N,N-dimethylaminobenzyl;

[0343] diphenylamidoborane-bis-η⁵-cyclopentadienyl zirconium allyl;

[0344] diphenylamidoborane-bis-η⁵-cyclopentadienyl zirconiumη⁴-1,4-diphenyl-1,3-butadiene;

[0345] diphenylamidoborane-bis-η⁵-cyclopentadienyl zirconiumη⁴-2,4-hexadiene;

[0346] diphenylamidoborane-bis-η⁵-cyclopentadienyl zirconiumη⁴-1,4-dinaphthyl-1,3-butadiene;

[0347] diphenylamidoborane-bis-η⁵-cyclopentadienyl zirconiumη⁴-phenyl-1,3-pentadiene;

[0348] diphenylamidoborane-bis-η⁵-cyclopentadienyl zirconiumη⁵-1,3-pentadiene;

[0349] diphenylamidoborane-bis-η⁵-n-butylcyclopentadienyl zirconiumdichloride;

[0350] diphenylamidoborane-bis-η⁵-n-butylcyclopentadienyl zirconiumdimethyl;

[0351] diphenylamidoborane-bis-η⁵-n-butylcyclopentadienyl zirconiumbis-dimethylamide;

[0352] diphenylamidoborane-bis-η⁵-n-butylcyclopentadienyl zirconium2-methyl-1,3-butadiene;

[0353] diphenylamidoborane-bis-η⁵-n-butylcyclopentadienyl zirconium2,3-dimethyl-1,3-butadiene;

[0354] diphenylamidoborane-bis-η⁵-n-butylcyclopentadienyl zirconium2-N,N-dimethylaminobenzyl;

[0355] diphenylamidoborane-bis-η⁵-n-butylcyclopentadienyl zirconiumallyl;

[0356] diphenylamidoborane-bis-η⁵-n-butylcyclopentadienyl zirconiumη⁴-1,4-diphenyl-1,3-butadiene;

[0357] diphenylamidoborane-bis-η⁵-n-butylcyclopentadienyl zirconiumη⁴-2,4-hexadiene;

[0358] diphenylamidoborane-bis-η⁵-n-butylcyclopentadienyl zirconiumη⁴-1,4-dinaphthyl-1,3-butadiene;

[0359] diphenylamidoborane-bis-η⁵-n-butylcyclopentadienyl zirconiumη⁴-1-phenyl-1,3-pentadiene;

[0360] diphenylamidoborane-bis-η⁵-n-butylcyclopentadienyl zirconiumη⁴-1,3-pentadiene;

[0361] diphenylamidoborane-bis-η⁵-inden-1-ylzirconium dichloride;

[0362] diphenylamidoborane-bis-η⁵-inden-1-ylzirconium dimethyl;

[0363] diphenylamidoborane-bis-η⁵-inden-1-ylzirconium bis-dimethylamide;

[0364] diphenylamidoborane-bis-η⁵-inden-1-ylzirconium2-methyl-1,3-butadiene;

[0365] diphenylamidoborane-bis-η⁵-inden-1-ylzirconium2,3-dimethyl-1,3-butadiene;

[0366] diphenylamidoborane-bis-η⁵-inden-1-ylzirconium2-N,N-dimethylaminobenzyl;

[0367] diphenylamidoborane-bis-η⁵-inden-1-ylzirconium allyl;

[0368] diphenylamidoborane-bis-η⁵-inden-1-ylzirconiumη⁴-1,4-diphenyl-1,3-butadiene;

[0369] diphenylamidoborane-bis-η⁵-inden-1-ylzirconium η⁴-2,4-hexadiene;

[0370] diphenylamidoborane-bis-η⁵-inden-1-ylzirconiumη⁴-1,4-dinaphthyl-1,3-butadiene;

[0371] diphenylamidoborane-bis-η⁵-inden-1-ylzirconium η⁴l-1-phenyl-1,3-pentadiene;

[0372] diphenylamidoborane-bis-η⁵-inden-1-ylzirconium η⁴-1,3-pentadiene;

[0373] diphenylamidoborane-bis-η⁵-(2-methylinden-1-yl)zirconiumdichloride;

[0374] diphenylamidoborane-bis-η⁵-(2-methylinden-1-yl)zirconiumdimethyl;

[0375] diphenylamidoborane-bis-η⁵-(2-methylinden-1-yl)zirconiumbis-dimethylamide;

[0376] diphenylamidoborane-bis-η⁵-(2-methylinden-1-yl)zirconium2-methyl-1,3-butadiene;

[0377] diphenylamidoborane-bis-η⁵-(2-methylinden-1-yl)zirconium2,3-dimethyl-1,3-butadiene;

[0378] diphenylamidoborane-bis-η⁵-(2-methylinden-1-yl)zirconium2-N,N-dimethylaminobenzyl;

[0379] diphenylamidoborane-bis-η⁵-(2-methylinden-1-yl)zirconium allyl;

[0380] diphenylamidoborane-bis-η⁵-(2-methylinden-1-yl)zirconiumη⁴-1,4-diphenyl-1,3-butadiene;

[0381] diphenylamidoborane-bis-η⁵-(2-methylinden-1-yl)zirconiumη⁴-2,4-hexadiene;

[0382] diphenylamidoborane-bis-η⁵-(2-methylinden-1-yl)zirconiumη⁴-1,4-dinaphthyl-1,3-butadiene;

[0383] diphenylamidoborane-bis-η⁵-(2-methylinden-1-yl)zirconiumη⁴-1-phenyl-1,3-pentadiene;

[0384] diphenylamidoborane-bis-η⁵-(2-methylinden-1-yl)zirconium4-1,3-pentadiene;

[0385] diphenylamidoborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconiumdichloride;

[0386] diphenylamidoborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconiumdimethyl;

[0387] diphenylamidoborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconiumbis-dimethylamide;

[0388] diphenylamidoborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconium2-methyl-1,3-butadiene;

[0389] diphenylamidoborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconium2,3-dimethyl-1,3-butadiene;

[0390] diphenylamidoborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconium2-N,N-dimethylaminobenzyl;

[0391] diphenylamidoborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconiumallyl;

[0392] diphenylamidoborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconiumη⁴-1,4-diphenyl-1,3-butadiene;

[0393] diphenylamidoborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconiumη⁴-2,4-hexadiene;

[0394] diphenylamidoborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconiumη⁴-1,4-dinaphthyl-1,3-butadiene;

[0395] diphenylamidoborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconiumη⁴-1-phenyl-1,3-pentadiene;

[0396] diphenylamidoborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconiumη⁴-1,3-pentadiene;

[0397] diphenylamidoborane-bis-η⁵-(2-ethyl-4-phenylinden-1-yl)zirconiumdichloride;

[0398] diphenylamidoborane-bis-η⁵-(2-ethyl-4-phenylinden-1-yl)zirconiumdimethyl;

[0399] diphenylamidoborane-bis-η⁵-(2-ethyl-4-phenylinden-1-yl)zirconiumbis-dimethylamide;

[0400] diphenylamidoborane-bis-η⁵-(2-ethyl-4-phenylinden-1-yl)zirconium2-methyl-1,3-butadiene;

[0401] diphenylamidoborane-bis-η⁵-(2-ethyl-4-phenylinden-1-yl)zirconium2,3-dimethyl-1,3-butadiene;

[0402] diphenylamidoborane-bis-η⁵-(2-ethyl-4-phenylinden-1-yl)zirconium2-N,N-dimethylaminobenzyl;

[0403] diphenylamidoborane-bis-η⁵-(2-ethyl-4-phenylinden-1-yl)zirconiumallyl;

[0404] diphenylamidoborane-bis-η⁵-(2-ethyl-4-phenylinden-1-yl)zirconiumη⁴-1,4-diphenyl-1,3-butadiene;

[0405] diphenylamidoborane-bis-η⁵-(2-ethyl-4-phenylinden-1-yl)zirconiumη⁴-2,4-hexadiene;

[0406] diphenylamidoborane-bis-η⁵-(2-ethyl-4-phenylinden-1-yl)zirconiumη⁴-1,4-dinaphthyl-1,3-butadiene;

[0407] diphenylamidoborane-bis-η⁵-(2-ethyl-4-phenylinden-1-yl)zirconiumη⁴-1-phenyl-1,3-pentadiene;

[0408] diphenylamidoborane-bis-η⁵-(2-ethyl-4-phenylinden-1-yl)zirconiumη⁴-1,3-pentadiene;

[0409]diphenylamidoborane-bis-η⁵-(2-isopropyl-4-phenylinden-1-yl)zirconiumdichloride;

[0410]diphenylamidoborane-bis-η⁵-(2-isopropyl-4-phenylinden-1-yl)zirconiumdimethyl;

[0411]diphenylamidoborane-bis-η⁵-(2-isopropyl-4-phenylinden-1-yl)zirconiumbis-dimethylamide;

[0412]diphenylamidoborane-bis-η⁵-(2-isopropyl-4-phenylinden-1-yl)zirconium2-methyl-1,3-butadiene;

[0413]diphenylamidoborane-bis-η⁵-(2-isopropyl-4-phenylinden-1-yl)zirconium2,3-dimethyl-1,3-butadiene;

[0414]diphenylamidoborane-bis-η⁵-(2-isopropyl-4-phenylinden-1-yl)zirconium2-N,N-dimethylaminobenzyl;

[0415]diphenylamidoborane-bis-η⁵-(2-isopropyl-4-phenylinden-1-yl)zirconiumallyl;

[0416]diphenylamidoborane-bis-η⁵-(2-isopropyl-4-phenylinden-1-yl)zirconiumη⁴-1,4-diphenyl-1,3-butadiene;

[0417]diphenylamidoborane-bis-η⁵-(2-isopropyl-4-phenylinden-1-yl)zirconiumη⁴-2,4-hexadiene;

[0418]diphenylamidoborane-bis-η⁵-(2-isopropyl-4-phenylinden-1-yl)zirconiumη⁴-1,4-dinaphthyl-1,3-butadiene;

[0419]diphenylamidoborane-bis-η⁵-(2-isopropyl-4-phenylinden-1-yl)zirconiumη⁴-1-phenyl-1,3-pentadiene;

[0420]diphenylamidoborane-bis-η⁵-(2-isopropyl-4-phenylinden-1-yl)zirconiumη⁴-1,3-pentadiene;

[0421]diphenylamidoborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)zirconiumdichloride;

[0422]diphenylamidoborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)zirconiumdimethyl;

[0423]diphenylamidoborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)zirconiumbis-dimethylamide;

[0424]diphenylamidoborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)zirconium2-methyl-1,3-butadiene;

[0425]diphenylamidoborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)zirconium2,3-dimethyl-1,3-butadiene;

[0426]diphenylamidoborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)zirconium2-N,N-dimethylaminobenzyl;

[0427]diphenylamidoborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)zirconiumallyl;

[0428]diphenylamidoborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)zirconiumη⁴-1,4-diphenyl-1,3-butadiene;

[0429]diphenylamidoborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)zirconiumη⁴-2,4-hexadiene;

[0430]diphenylamidoborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)zirconiumη⁴-1,4-dinaphthyl-1,3-butadiene;

[0431]diphenylamidoborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)zirconiumη⁴-1-phenyl-1,3-pentadiene;

[0432]diphenylamidoborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)zirconiumη⁴-1,3-pentadiene;

[0433]diphenylamidoborane-bis-η⁵-(2-methyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconiumdichloride;

[0434]diphenylamidoborane-bis-η⁵-(2-methyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconiumdimethyl;

[0435]diphenylamidoborane-bis-η⁵-(2-methyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconiumbis-dimethylamide;

[0436]diphenylamidoborane-bis-η⁵-(2-methyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium2-methyl-1,3-butadiene;

[0437]diphenylamidoborane-bis-η⁵-(2-methyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium2,3-dimethyl-1,3-butadiene;

[0438]diphenylamidoborane-bis-η⁵-(2-methyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium2-N,N-dimethylaminobenzyl;

[0439]diphenylamidoborane-bis-η⁵-(2-methyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconiumallyl;

[0440]diphenylamidoborane-bis-η⁵-(2-methyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconiumη⁴-1,4-diphenyl-1,3-butadiene;

[0441]diphenylamidoborane-bis-η⁵-(9-methyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconiumη⁴-2,4-hexadiene;

[0442]diphenylamidoborane-bis-η⁵-(2-methyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconiumη⁴-1,4-dinaphthyl-1,3-butadiene;

[0443]diphenylamidoborane-bis-η⁵-(2-methyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconiumη⁴-1-phenyl-1,3-pentadiene;

[0444]diphenylamidoborane-bis-η⁵-(2-methyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconiumη⁴-1,3-pentadiene;

[0445]diphenylamidoborane-bis-η⁵-(2-ethyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconiumdichloride;

[0446]diphenylamidoborane-bis-η⁵-(2-ethyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconiumdimethyl;

[0447]diphenylamidoborane-bisη⁵(2-ethyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconiumbis-dimethylamide;

[0448]diphenylamidoborane-bis-η⁵-(2-ethyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium2-methyl-1,3-butadiene;

[0449]diphenylamidoborane-bis-η⁵-(2-ethyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium2,3-dimethyl-1,3-butadiene;

[0450]diphenylamidoborane-bis-η⁵-(2-ethyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium2-N,N-dimethylaminobenzyl;

[0451]diphenylamidoborane-bis-η⁵-(2-ethyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconiumallyl;

[0452]diphenylamidoborane-bis-η⁵-(2-ethyl-4bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconiumη⁴-1,4-diphenyl-1,3-butadiene;

[0453]diphenylamidoborane-bis-η⁵-(2-ethyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconiumη⁴-2,4-hexadiene;

[0454]diphenylamidoborane-bis-η⁵-(2-ethyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconiumη⁴-1,4-dinaphthyl-1,3-butadiene;

[0455]diphenylamidoborane-bis-η⁵-(2-ethyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconiumη⁴-1-phenyl-1,3-pentadiene;

[0456]diphenylamidoborane-bis-η⁵-(2-ethyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconiumη⁴-1,3-pentadiene;

[0457]diphenylamidoborane-bis-η⁵-(2-isopropyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconiumdichloride;

[0458]diphenylamidoborane-bis-η⁵-(2-isopropyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconiumdimethyl;

[0459]diphenylamidoborane-bis-η⁵-(2-isopropyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconiumbis-dimethylamide;

[0460]diphenylamidoborane-bis-η⁵-(2-isopropyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium2-methyl-1,3-butadiene;

[0461] diphenylamidoborane-bis-η⁵-(2-isopropyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium 2,3-dimethyl-1,3-butadiene;

[0462]diphenylamidoborane-bis-η⁵-(2-isopropyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium2-N,N-dimethylaminobenzyl;

[0463]diphenylamidoborane-bis-η⁵-(2-isopropyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconiumallyl;

[0464]diphenylamidoborane-bis-η⁵-(2-isopropyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconiumη⁴-1,4-diphenyl-1,3-butadiene;

[0465]diphenylamidoborane-bis-η⁵-(2-isopropyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconiumη⁴-2,4-hexadiene;

[0466]diphenylamidoborane-bis-η⁵-(2-isopropyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconiumη⁴-1,4-dinaphthyl-1,3-butadiene;

[0467]diphenylamidoborane-bis-η⁵-(2-isopropyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconiumη⁴-1-phenyl-1,3-pentadiene;

[0468]diphenylamidoborane-bis-η⁵-(2-isopropyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconiumη⁴-1,3-pentadiene;

[0469] diphenylamidoborane-bis-η⁵-(3-isopropylinden-1-yl)zirconiumdichloride;

[0470] diphenylamidoborane-bis-η⁵-(3-isopropylinden-1-yl)zirconiumdimethyl;

[0471] diphenylamidoborane-bis-η⁵-(3-isopropylinden-1-yl)zirconiumbis-dimethylamide;

[0472] diphenylamidoborane-bis-η⁵-(3-isopropylinden-1-yl)zirconium2-methyl-1,3-butadiene;

[0473] diphenylamidoborane-bis-η⁵-(3-isopropylinden-1-yl)zirconium2,3-dimethyl-1,3-butadiene;

[0474] diphenylamidoborane-bis-η⁵-(3-isopropylinden-1-yl)zirconium2-N,N-dimethylaminobenzyl;

[0475] diphenylamidoborane-bis-η⁵-(3-isopropylinden-1-yl)zirconiumallyl;

[0476] diphenylamidoborane-bis-η⁵-(3-isopropylinden-1-yl)zirconiumη⁴-1,4-diphenyl-1,3-butadiene;

[0477] diphenylamidoborane-bis-η⁵-(3-isopropylinden-1-yl)zirconiumη⁴-2,4-hexadiene;

[0478] diphenylamidoborane-bis-η⁵-(3-isopropylinden-1-yl)zirconiumη⁴-1,4-dinaphthyl-1,3-butadiene;

[0479] diphenylamidoborane-bis-η⁵-(3-isopropylinden-1-yl)zirconiumη⁴-1-phenyl-1,3-pentadiene;

[0480] diphenylamidoborane-bis-η⁵-(3-isopropylinden-1-yl)zirconiumη⁴-1,3-pentadiene;

[0481] diphenylamidoborane-bis-η⁵-(3-t-butylinden-1-yl)zirconiumdichloride;

[0482] diphenylamidoborane-bis-η⁵-(3-t-butylinden-1-yl)zirconiumdimethyl;

[0483] diphenylamidoborane-bis-η⁵-(3-t-butylinden-1-yl)zirconiumbis-dimethylamide;

[0484] diphenylamidoborane-bis-η⁵-(3-t-butylinden-1-yl)zirconium2-methyl-1,3-butadiene;

[0485] diphenylamidoborane-bis-η⁵-(3-t-butylinden-1-yl)zirconium2,3-dimethyl-1,3-butadiene;

[0486] diphenylamidoborane-bis-η⁵-(3-t-butylinden-1-yl)zirconium2-N,N-dimethylaminobenzyl;

[0487] diphenylamidoborane-bis-η⁵-(3-t-butylinden-1-yl)zirconium allyl;

[0488] diphenylamidoborane-bis-η⁵-(3-t-butylinden-1-yl)zirconiumη⁴-1,4-diphenyl-1,3-butadiene;

[0489] diphenylamidoborane-bis-η⁵-(3-t-butylinden-1-yl)zirconiumη⁴-2,4-hexadiene;

[0490] diphenylamidoborane-bis-η⁵-(3-t-butylinden-1-yl)zirconiumη⁴-1,4-dinaphthyl-1,3-butadiene;

[0491] diphenylamidoborane-bis-η⁵-(3-t-butylinden-1-yl)zirconiumη⁴-1-phenyl-1,3-pentadiene;

[0492] diphenylamidoborane-bis-η⁵-(3-t-butylinden-1-yl)zirconiumη⁴-1,3-pentadiene;

[0493] bis(trimethylsilyl)amidoborane-bis-η⁵-cyclopentadienylzirconiumdichloride;

[0494] bis(trimethylsilyl)amidoborane-bis-η⁵-cyclopentadienylzirconiumdimethyl;

[0495] bis(trimethylsilyl)amidoborane-bis-η⁵-cyclopentadienylzirconiumbis-dimethylamide;

[0496] bis(trimethylsilyl)amidoborane-bis-η⁵-cyclopentadienylzirconium2-methyl-1,3-butadiene;

[0497] bis(trimethylsilyl)amidoborane-bis-η⁵-cyclopentadienylzirconium2,3-dimethyl-1,3-butadiene;

[0498] bis(trimethylsilyl)amidoborane-bis-η⁵-cyclopentadienylzirconium2-N,N-dimethylaminobenzyl;

[0499] bis(trimethylsilyl)amidoborane-bis-η⁵-cyclopentadienylzirconiumallyl;

[0500] bis(trimethylsilyl)amidoborane-bis-η⁵-cyclopentadienylzirconiumη⁴-1,4-diphenyl-1,3-butadiene;

[0501] bis(trimethylsilyl)amidoborane-bis-η⁵-cyclopentadienylzirconiumη⁴-2,4-hexadiene;

[0502] bis(trimethylsilyl)amidoborane-bis-η⁵-cyclopentadienylzirconiumη⁴-dinaphthyl-1,3-butadiene;

[0503] bis(trimethylsilyl)amidoborane-bis-η⁵-cyclopentadienylzirconiumη⁴-1-phenyl-1,3-pentadiene;

[0504] bis(trimethylsilyl)amidoborane-bis-η⁵-cyclopentadienylzirconiumη⁴-1,3-pentadiene;

[0505] bis(trimethylsilyl)amidoborane-bis-η⁵-inden-1-ylzirconiumdichloride;

[0506] bis(trimethylsilyl)amidoborane-bis-η⁵-inden-1-ylzirconiumdimethyl;

[0507] bis(trimethylsilyl)amidoborane-bis-η⁵-inden-1-ylzirconiumbis-dimethylamide;

[0508] bis(trimethylsilyl)amidoborane-bis-η⁵-inden-1-ylzirconium2-methyl-1,3-butadiene;

[0509] bis(trimethylsilyl)amidoborane-bis-η⁵-inden-1-ylzirconium2,3-dimethyl-1,3-butadiene;

[0510] bis(trimethylsilyl)amidoborane-bis-η⁵-inden-1-ylzirconium2-N,N-dimethylaminobenzyl;

[0511] bis(trimethylsilyl)amidoborane-bis-η⁵-inden-1-ylzirconium allyl;

[0512] bis(trimethylsilyl)amidoborane-bis-η⁵-inden-1-ylzirconiumη⁴-1,4-diphenyl-1,3-butadiene;

[0513] bis(trimethylsilyl)amidoborane-bis-η⁵-inden-1-ylzirconiumη⁴-2,4-hexadiene;

[0514] bis(trimethylsilyl)amidoborane-bis-η⁵-inden-1-ylzirconiumη⁴-1,4-dinaphthyl-1,3-butadiene;

[0515] bis(trimethylsilyl)amidoborane-bis-η⁵-inden-1-ylzirconiumη⁴-1-phenyl-1,3-pentadiene;

[0516] bis(trimethylsilyl)amidoborane-bis-η⁵-inden-1-ylzirconiumη⁴-1,3-pentadiene;

[0517]bis(trimethylsilyl)amidoborane-bis-η⁵-(2-methylinden-1-yl)zirconiumdichloride;

[0518]bis(trimethylsilyl)amidoborane-bis-η⁵-(2-methylinden-1-yl)zirconiumdimethyl;

[0519]bis(trimethylsilyl)amidoborane-bis-η⁵-(2-methylinden-1-yl)zirconiumbis-dimethylamide;

[0520]bis(trimethylsilyl)amidoborane-bis-η⁵-(2-methylinden-1-yl)zirconium2-methyl-1,3-butadiene;

[0521]bis(trimethylsilyl)amidoborane-bis-η⁵-(2-methylinden-1-yl)zirconium2,3-dimethyl-1,3-butadiene;

[0522]bis(trimethylsilyl)amidoborane-bis-η⁵-(2-methylinden-1-yl)zirconium2-N,N-dimethylaminobenzyl;

[0523] bis(trimethylsilyl)amidoborane-bis-η⁵(2-methylinden1-yl)zirconiumallyl;

[0524]bis(trimethylsilyl)amidoborane-bis-η⁵-(2-methylinden-1-yl)zirconiumη⁴-1,4-diphenyl-1,3-butadiene;

[0525]bis(trimethylsilyl)amidoborane-bis-η⁵-(2-methylinden-1-yl)zirconiumη⁴-2,4-hexadiene;

[0526]bis(trimethylsilyl)amidoborane-bis-η⁵-(2-methylinden-1-yl)zirconiumη⁴-1,4-dinaphthyl-1,3-butadiene;

[0527]bis(trimethylsilyl)amidoborane-bis-η⁵-(2-methylinden-1-yl)zirconiumη⁴-1-phenyl-1,3-pentadiene;

[0528]bis(trimethylsilyl)amidoborane-bis-η⁵-(2-methylinden-1-yl)zirconiumη⁴-1,3-pentadiene;

[0529]bis(trimethylsilyl)amidoborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconiumdichloride;

[0530]bis(trimethylsilyl)amidoborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconiumdimethyl;

[0531]bis(trimethylsilyl)amidoborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconiumbis-dimethylamide;

[0532]bis(trimethylsilyl)amidoborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconium2-methyl-1,3-butadiene;

[0533]bis(trimethylsilyl)amidoborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconium2,3-dimethyl-1,3-butadiene;

[0534]bis(trimethylsilyl)amidoborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconium2-N,N-dimethylaminobenzyl;

[0535]bis(trimethylsilyl)amidoborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconiumallyl;

[0536]bis(trimethylsilyl)amidoborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconiumη⁴-1,4-diphenyl-1,3-butadiene;

[0537]bis(trimethylsilyl)amidoborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconiumη⁴-2,4-hexadiene;

[0538]bis(trimethylsilyl)amidoborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconiumη⁵-1,4-dinaphthyl-1,3-butadiene;

[0539]bis(trimethylsilyl)amidoborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconiumη⁴-1-phenyl-1,3-pentadiene;

[0540]bis(trimethylsilyl)amidoborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconiumη⁴-1,3-pentadiene;

[0541]bis(trimethylsilyl)amidoborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)zirconiumdichloride;

[0542]bis(trimethylsilyl)amidoborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)zirconiumdimethyl;

[0543]bis(trimethylsilyl)amidoborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)zirconiumbis-dimethylamide;

[0544]bis(trimethylsilyl)amidoborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)zirconium2-methyl-1,3-butadiene;

[0545]bis(trimethylsilyl)amidoborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)zirconium2,3-dimethyl-1,3-butadiene;

[0546]bis(trimethylsilyl)amidoborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)zirconium2-N,N-dimethylaminobenzyl;

[0547]bis(trimethylsilyl)amidoborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)zirconiumallyl;

[0548]bis(trimethylsilyl)amidoborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)zirconiumη⁴-1,4-diphenyl-1,3-butadiene;

[0549]bis(trimethylsilyl)amidoborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)zirconiumη⁴-2,4-hexadiene;

[0550]bis(trimethylsilyl)amidoborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)zirconiumη⁴-_(1,4)-dinaphthyl-1,3-butadiene;

[0551]bis(trimethylsilyl)amidoborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)zirconiumη⁴-1-phenyl-1,3-pentadiene;

[0552]bis(trimethylsilyl)amidoborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)zirconiumη⁴-1,3-pentadiene;

[0553]bis(trimethylsilyl)amidoborane-bis-η⁵-(3-isopropylinden-1-yl)zirconiumdichloride;

[0554]bis(trimethylsilyl)amidoborane-bis-η⁵-(3-isopropylinden-1-yl)zirconiumdimethyl;

[0555]bis(trimethylsilyl)amidoborane-bis-η⁵-(3-isopropylinden-1-yl)zirconiumbis-dimethylamide;

[0556]bis(trimethylsilyl)amidoborane-bis-η⁵-(3-isopropylinden-1-yl)zirconium2-methyl-1,3-butadiene;

[0557]bis(trimethylsilyl)amidoborane-bis-η⁵-(3-isopropylinden-1-yl)zirconium2,3-dimethyl-1,3-butadiene;

[0558]bis(trimethylsilyl)amidoborane-bis-η⁵-(3-isopropylinden-1-yl)zirconium2-N,N-dimethylaminobenzyl;

[0559]bis(trimethylsilyl)amidoborane-bis-η⁵-(3-isopropylinden-1-yl)zirconiumallyl;

[0560]bis(trimethylsilyl)amidoborane-bis-η⁵-(3-isopropylinden-1-yl)zirconiumη⁴-1,4-diphenyl-1,3-butadiene;

[0561]bis(trimethylsilyl)amidoborane-bis-η⁵-(3-isopropylinden-1-yl)zirconiumη⁴-2,4-hexadiene;

[0562]bis(trimethylsilyl)amidoborane-bis-η⁵-(3-isopropylinden-1-yl)zirconiumη⁴-1,4-dinaphthyl-1,3-butadiene;

[0563]bis(trimethylsilyl)amidoborane-bis-η⁵-(3-isopropylinden-1-yl)zirconiumη⁴-1-phenyl-1,3-pentadiene;

[0564]bis(trimethylsilyl)amidoborane-bis-η⁵-(3-isopropylinden-1-yl)zirconiumη⁴-1,3-pentadiene;

[0565]bis(trimethylsilyl)amidoborane-bis-η⁵-(3-t-butylinden-1-yl)zirconiumdichloride;

[0566]bis(trimethylsilyl)amidoborane-bis-η⁵-(3-t-butylinden-1-yl)zirconiumdimethyl;

[0567]bis(trimethylsilyl)amidoborane-bis-η⁵-(3-t-butylinden-1-yl)zirconiumbis-dimethylamide;

[0568]bis(trimethylsilyl)amidoborane-bis-η⁵-(3-t-butylinden-1-yl)zirconium2-methyl-1,3-butadiene;

[0569]bis(trimethylsilyl)amidoborane-bis-η⁵-(3-t-butylinden-1-yl)zirconium2,3-dimethyl-1,3-butadiene;

[0570]bis(trimethylsilyl)amidoborane-bis-η⁵-(3-t-butylinden-1-yl)zirconium2-N,N-dimethylaminobenzyl;

[0571]bis(trimethylsilyl)amidoborane-bis-η⁵-(3-t-butylinden-1-yl)zirconiumallyl;

[0572]bis(trimethylsilyl)amidoborane-bis-η⁵-(3-t-butylinden-1-yl)zirconiumη⁴-1,4-diphenyl-1,3-butadiene;

[0573]bis(trimethylsilyl)amidoborane-bis-η⁵-(3-t-butylinden-1-yl)zirconiumη⁴-2,4-hexadiene;

[0574]bis(trimethylsilyl)amidoborane-bis-η⁵-(3-t-butylinden-1-yl)zirconiumη⁴-1,4-dinaphthyl-1,3-butadiene;

[0575]bis(trimethylsilyl)amidoborane-bis-η⁵-(3-t-butylinden-1-yl)zirconiumη⁴-1-phenyl-1,3-pentadiene;

[0576]bis(trimethylsilyl)amidoborane-bis-η⁵-(3-t-butylinden-1-yl)zirconiumη⁴-1,3-pentadiene;

[0577]bis(diisopropylamido)diborane-1,2-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconiumdichloride;

[0578]bis(diisopropylamido)diborane-1,2-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconiumdimethyl;

[0579]bis(diisopropylamido)diborane-1,2-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconiumbis-dimethylamide;

[0580]bis(diisopropylamido)diborane-1,2-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconium2-methyl-1,3-butadiene;

[0581]bis(diisopropylamido)diborane-1,2-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconium2,3-dimethyl-1,3-butadiene; ;

[0582]bis(diisopropylamido)diborane-1,2-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconium2-N,N-dimethylaminobenzyl;

[0583]bis(diisopropylamido)diborane-1,2-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconiumallyl;

[0584]bis(diisopropylamido)diborane-1,2-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconiumη⁴-1,4-diphenyl-1,3-butadiene;

[0585]bis(diisopropylamido)diborane-1,2-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconiumη⁴-2,4-hexadiene;

[0586]bis(diisopropylamido)diborane-1,2-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconiumη⁴-1,4-dinaphthyl-1,3-butadiene;

[0587]bis(diisopropylamido)diborane-1,2-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconiumη⁴-1-phenyl-1,3-pentadiene;

[0588]bis(diisopropylamido)diborane-1,2-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconiumη⁴-1,3-pentadiene;

[0589] dimethylamidoborane-bis-η⁵-cyclopentadienyl hafnium dichloride;

[0590] dimethylamidoborane-bis-η⁵-cyclopentadienyl hafnium dimethyl;

[0591] dimethylamidoborane-bis-η⁵-cyclopentadienyl hafniumbis-dimethylamide;

[0592] dimethylamidoborane-bis-η⁵-cyclopentadienyl hafnium2-methyl-1,3-butadiene;

[0593] dimethylamidoborane-bis-η⁵-cyclopentadienyl hafnium2;3dinaphthyl-1,3-butadiene;

[0594] dimethylamidoborane-bis-η⁵-cyclopentadienyl hafnium2-N,N-dimethylaminobenzyl;

[0595] dimethylamidoborane-bis-η⁵-cyclopentadienyl hafnium allyl;

[0596] dimethylamidoborane-bis-η⁵-cyclopentadienyl hafniumη⁴-1,4-diphenyl-1,3-butadiene;

[0597] dimethylamidoborane-bis-η⁵-cyclopentadienyl hafniumη⁴-2,4-hexadiene;

[0598] dimethylamidoborane-bis-η⁵-cyclopentadienyl hafniumη⁴-1,4-dinaphthyl-1,3-butadiene;

[0599] dimethylamidoborane-bis-η⁵-cyclopentadienyl hafniumη⁴-1-phenyl-1,3-pentadiene;

[0600] dimethylamidoborane-bis-η⁵-cyclopentadienyl hafniumη⁴-1,3-pentadiene;

[0601] dimethylamidoborane-bis-η⁵-n-butylcyclopentadienyl hafniumdichloride;

[0602] dimethylamidoborane-bis-η⁵-n-butylcyclopentadienyl hafniumdimethyl;

[0603] dimethylamidoborane-bis-η⁵-n-butylcyclopentadienyl hafniumbis-dimethylamide;

[0604] dimethylamidoborane-bis-η⁵-n-butylcyclopentadienyl hafnium2-methyl-1,3-butadiene;

[0605] dimethylamidoborane-bis-η⁵-n-butylcyclopentadienyl hafnium2,3-dimethyl-1,3-butadiene;

[0606] dimethylamidoborane-bis-η⁵-n-butylcyclopentadienyl hafnium2-N,N-dimethylaminobenzyl;

[0607] dimethylamidoborane-bis-η⁵-n-butylcyclopentadienyl hafnium allyl;

[0608] dimethylamidoborane-bis-η⁵-n-butylcyclopentadienyl hafniumη⁴-1,4-diphenyl-1,3-butadiene;

[0609] dimethylamidoborane-bis-η⁵-n-butylcyclopentadienyl hafniumη⁴-2,4-hexadiene;

[0610] dimethylamidoborane-bis-η⁵-n-butylcyclopentadienyl hafniumη⁴-1,4-dinaphthyl-1,3-butadiene;

[0611] dimethylamidoborane-bis-η⁵-n-butylcyclopentadienyl hafniumη⁴-1-phenyl-1,3-pentadiene;

[0612] dimethylamidoborane-bis-η⁵-n-butylcyclopentadienyl hafniumη⁴-1,3-pentadiene;

[0613] dimethylamidoborane-bis-η⁵-inden-1-ylhafnium dichloride;

[0614] dimethylamidoborane-bis-η⁵-inden-1-ylhafnium dimethyl;

[0615] dimethylamidoborane-bis-η⁵-inden-1-ylhafnium bis-dimethylamide;

[0616] dimethylamidoborane-bis-η⁵-inden-1-ylhafnium2-methyl-1,3-butadiene;

[0617] dimethylamidoborane-bis-η⁵-inden-1-ylhafnium2,3-dimethyl-1,3-butadiene;

[0618] dimethylamidoborane-bis-η⁵-inden-1-ylhafnium2-N,N-dimethylaminobenzyl;

[0619] dimethylamidoborane-bis-η⁵-inden-1-ylhafnium allyl;

[0620] dimethylamidoborane-bis-η⁵-inden-1-ylhafniumη⁴-1,4-diphenyl-1,3-butadiene;

[0621] dimethylamidoborane-bis-η⁵-inden-1-ylhafnium η⁴-2,4-hexadiene;

[0622] dimethylamidoborane-bis-η⁵-inden-1-ylhafniumη⁴-1,4-dinaphthyl-1,3-butadiene;

[0623] dimethylamidoborane-bis-η⁵-inden-1-ylhafniumη⁴-1-phenyl-1,3-pentadiene;

[0624] dimethylamidoborane-bis-η⁵-inden-1-ylhafnium η⁴-1,3-pentadiene;

[0625] dimethylamidoborane-bis-η⁵-(2-methylinden-1-yl)hafniumdichloride;

[0626] dimethylamidoborane-bis-η⁵-(2-methylinden-1-y)hafnium dimethyl;

[0627] dimethylamidoborane-bis-η⁵-(2-methylinden-1-yl)hafniumbis-dimethylamide;

[0628] dimethylamidoborane-bis-η⁵-(2-methylinden-1-yl)hafnium2-methyl-1,3-butadiene;

[0629] dimethylamidoborane-bis-η⁵-(2-methylinden-1-yl)hafnium2,3-dimethyl-1,3-butadiene;

[0630] dimethylamidoborane-bis-η⁵-(2-methylinden-1-yl)hafnium2-N,N-dimethylaminobenzyl;

[0631] dimethylamidoborane-bis-η⁵-(2-methylinden-1-yl)hafnium allyl;

[0632] dimethylamidoborane-bis-η⁵-(2-methylinden-1-yl)hafniumη⁴-1,4-diphenyl-1,3-butadiene;

[0633] dimethylamidoborane-bis-η⁵-(2-methylinden-1-yl)hafniumη⁴-2,4-hexadiene;

[0634] dimethylamidoborane-bis-η⁵-(2-methylinden-1-yl)hafniumη⁴-1,4-dinaphthyl-1,3-butadiene;

[0635] dimethylamidoborane-bis-η⁵-(2-methylinden-1-yl)hafniumη⁴-1-phenyl-1,3-pentadiene;

[0636] dimethylamidoborane-bis-η⁵-(2-methylinden-1-yl)hafniumη⁴-1,3-pentadiene;

[0637] dimethylamidoborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)hafniumdichloride;

[0638] dimethylamidoborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)hafniumdimethyl;

[0639] dimethylamidoborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)hafniumbis-dimethylamide;

[0640] dimethylamidoborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)hafnium2-methyl-1,3-butadiene;

[0641] dimethylamidoborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)hafnium2,3-dimethyl-1,3-butadiene;

[0642] dimethylamidoborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)hafnium2-N,N-dimethylaminobenzyl;

[0643] dimethylamidoborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)hafniumallyl;

[0644] dimethylamidoborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)hafniumη⁴-1,4-diphenyl-1,3-butadiene;

[0645] dimethylamidoborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)hafniumη⁴-2,4-hexadiene;

[0646] dimethylamidoborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)hafniumη⁴-1,4-dinaphthyl-1,3-butadiene;

[0647] dimethylamidoborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)hafniumη⁴-1-phenyl-1,3-pentadiene;

[0648] dimethylamidoborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)hafniumη⁴-1,3-pentadiene;

[0649] dimethylamidoborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)hafniumdichloride;

[0650] dimethylamidoborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)hafniumdimethyl;

[0651] dimethylamidoborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)hafniumbis-dimethylamide;

[0652] dimethylamidoborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)hafnium2-methyl-1,3-butadiene;

[0653] dimethylamidoborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)hafnium2,3-dimethyl-1,3-butadiene;

[0654] dimethylamidoborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)hafnium2-N,N-dimethylaminobenzyl;

[0655] dimethylamidoborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)hafniumallyl;

[0656] dimethylamidoborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)hafniumη⁴-1,4-diphenyl-1,3-butadiene;

[0657] dimethylamidoborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)hafniumη⁴-2,4-hexadiene;

[0658] dimethylamidoborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)hafniumη⁴-1,4-dinaphthyl-1,3-butadiene;

[0659] dimethylamidoborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)hafniumη⁴-phenyl-1,3-pentadiene;

[0660] dimethylamidoborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)hafniumη⁴-1,3-pentadiene;

[0661] dimethylamidoborane-bis-η⁵-(3-isopropylinden-1-yl)hafniumdichloride;

[0662] dimethylamidoborane-bis-η⁵-(3-isopropylinden-1-yl)hafniumdimethyl;

[0663] dimethylamidoborane-bis-η⁵-(3-isopropylinden-1-yl)hafniumbis-dimethylamide;

[0664] dimethylamidoborane-bis-η⁵-(3-isopropylinden-1-yl)hafnium2-methyl-1,3-butadiene;

[0665] dimethylamidoborane-bis-η⁵-(3-isopropylinden-1-yl)hafnium2,3-dimethyl-1,3-butadiene;

[0666] dimethylamidoborane-bis-η⁵-(3-isopropylinden-1-yl)hafnium2-N,N-dimethylaminobenzyl;

[0667] dimethylamidoborane-bis-η⁵-(3-isopropylinden-1-yl)hafnium allyl;

[0668] dimethylamidoborane-bis-η⁵-(3-isopropylinden-1-yl)hafniumη⁴-1,4-diphenyl-1,3-butadiene;

[0669] dimethylamidoborane-bis-η⁵-(3-isopropylinden-1-yl)hafniumη⁴-2,4-hexadiene;

[0670] dimethylamidoborane-bis-η⁵-(3-isopropylinden-1-yl)hafniumη⁴-1,4-dinaphthyl-1,3-butadiene;

[0671] dimethylamidoborane-bis-η⁵-(3-isopropylinden-1-yl)hafniumη⁴-1-phenyl-1,3-pentadiene;

[0672] dimethylamidoborane-bis-η⁵-(3-isopropylinden-1-yl)hafnium1,3-pentadiene;

[0673] dimethylamidoborane-bis-η⁵-(3-t-butylinden-1-yl)hafniumdichloride;

[0674] dimethylamidoborane-bis-η⁵-(3-t-butylinden-1-yl)hafnium dimethyl;

[0675] dimethylamidoborane-bis-η⁵-(3-t-butylinden-1-yl)hafniumbis-dimethylamide;

[0676] dimethylamidoborane-bis-η⁵-(3-t-butylinden-1-yl)hafnium2-methyl-1,3-butadiene;

[0677] dimethylamidoborane-bis-η⁵-(3-t-butylinden-1-yl)hafnium2,3-dimethyl-1,3-butadiene;

[0678] dimethylamidoborane-bis-η⁵-(3-t-butylinden-1-yl)hafnium2-N,N-dimethylaminobenzyl;

[0679] dimethylamidoborane-bis-η⁵-(3-t-butylinden-1-yl)hafnium allyl;

[0680] dimethylamidoborane-bis-η⁵-(3-t-butylinden-1-yl)hafniumη⁴-_(1,4)-diphenyl-1,3-butadiene;

[0681] dimethylamidoborane-bis-η⁵-(3-t-butylinden-1-yl)hafniumη⁴-2,4-hexadiene;

[0682] dimethylamidoborane-bis-η⁵-(3-t-butylinden-1-yl)hafniumη⁴-1,4-dinaphthyl-1,3-butadiene;

[0683] dimethylamidoborane-bis-η⁵-(3-t-butylinden-1-yl)hafniumη⁴-phenyl-1,3-pentadiene;

[0684] dimethylamidoborane-bis-η⁵-(3-t-butylinden-1-yl)hafniumη⁴-1,3-pentadiene;

[0685] diisopropylamidoborane-bis-η⁵-cyclopentadienylhafnium dichloride;

[0686] diisopropylamidoborane-bis-η⁵-cyclopentadienylhafnium dimethyl;

[0687] diisopropylamidoborane-bis-η⁵-cyclopentadienylhafniumbis-dimethylamide;

[0688] diisopropylamidoborane-bis-η⁵-cyclopentadienylhafnium2-methyl-1,3-butadiene;

[0689] diisopropylamidoborane-bis-η⁵-cyclopentadienylhafnium2,3-dimethyl-1,3-butadiene;

[0690] diisopropylamidoborane-bis-η⁵-cyclopentadienylhafnium2-N,N-dimethylaminobenzyl;

[0691] diisopropylamidoborane-bis-η⁵-cyclopentadienylhafnium allyl;

[0692] diisopropylamidoborane-bis-η⁵-cyclopentadienylhafniumη⁴-1,4-diphenyl-1,3-butadiene;

[0693] diisopropylamidoborane-bis-η⁵-cyclopentadienylhafniumη⁴-2,4-hexadiene;

[0694] diisopropylamidoborane-bis-η⁵-cyclopentadienylhafniumη⁴-1,4-dinaphthyl-1,3-butadiene;

[0695] diisopropylamidoborane-bis-η⁵-cyclopentadienylhafniumη⁴-1-phenyl-1,3-pentadiene;

[0696] diisopropylamidoborane-bis-η⁵-cyclopentadienylhafniumη⁵-1,3-pentadiene;

[0697] diisopropylamidoborane-bis-η⁵-inden-1-ylhafnium dichloride;

[0698] diisopropylamidoborane-bis-η⁵-inden-1-ylhafnium dimethyl;

[0699] diisopropylamidoborane-bis-η⁵-inden-1-ylhafniumbis-dimethylamide;

[0700] diisopropylamidoborane-bis-η⁵-inden-1-ylhafnium2-methyl-1,3-butadiene;

[0701] diisopropylamidoborane-bis-η⁵-inden-1-ylhafnium2,3-dimethyl-1,3-butadiene;

[0702] diisopropylamidoborane-bis-η⁵-inden-1-ylhafnium2-N,N-dimethylaminobenzyl;

[0703] diisopropylamidoborane-bis-η⁵-inden-1-ylhafnium allyl;

[0704] diisopropylamidoborane-bis-η⁵-inden-1-ylhafniumη⁴-1,4-diphenyl-1,3-butadiene;

[0705] diisopropylamidoborane-bis-η⁵-inden-1-ylhafnium η⁴-2,4-hexadiene;

[0706] diisopropylamidoborane-bis-η⁵-inden-1-ylhafniumη⁴-1,4-dinaphthyl-1,3-butadiene;

[0707] diisopropylamidoborane-bis-η⁵-inden-1-ylhafniumη⁴-1-phenyl-1,3-pentadiene;

[0708] diisopropylamidoborane-bis-η⁵-inden-1-ylhafniumη⁴-1,3-pentadiene;

[0709] diisopropylamidoborane-bis-η⁵-(2-methylinden-1-yl)hafniumdichloride;

[0710] diisopropylamidoborane-bis-η⁵-(2-methylinden-1-yl)hafniumdimethyl;

[0711] diisopropylamidoborane-bis-η⁵-(2-methylinden-1-yl)hafniumbis-dimethylamide;

[0712] diisopropylamidoborane-bis-η⁵-(2-methylinden-1-yl)hafnium2-methyl-1,3-butadiene;

[0713] diisopropylamidoborane-bis-η⁵-(2-methylinden-1-yl)hafnium2,3-dimethyl-1,3-butadiene;

[0714] diisopropylamidoborane-bis-η⁵-(2-methylinden-1-yl)hafnium2-N,N-dimethylaminobenzyl;

[0715] diisopropylamidoborane-bis-η⁵-(2-methylinden-1-yl)hafnium allyl;

[0716] diisopropylamidoborane-bis-η⁵-(2-methylinden-1-yl)hafniumη⁴-1,4-diphenyl-1,3-butadiene;

[0717] diisopropylamidoborane-bis-η⁵-(2-methylinden-1-yl)hafniumη⁴-2,4-hexadiene;

[0718] diisopropylamidoborane-bis-η⁵-(2-methylinden-1-yl)hafniumη⁴-1,4-dinaphthyl-1,3-butadiene;

[0719] diisopropylamidoborane-bis-η⁵-(2-methylinden-1-yl)hafniumη⁴-1-phenyl-1,3-pentadiene;

[0720] diisopropylamidoborane-bis-η⁵-(2-methylinden-1-yl)hafniumη⁴-1,3-pentadiene;

[0721]diisopropylamidoborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)hafniumdichloride;

[0722]diisopropylamidoborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)hafniumdimethyl;

[0723]diisopropylamidoborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)hafniumbis-dimethylamide;

[0724]diisopropylamidoborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)hafnium2-methyl-1,3-butadiene;

[0725]diisopropylamidoborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)hafnium2,3-dimethyl-1,3-butadiene;

[0726]diisopropylamidoborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)hafnium2-N,N-dimethylaminobenzyl;

[0727]diisopropylamidoborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)hafniumallyl;

[0728]diisopropylamidoborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)hafniumη⁴-1,4-diphenyl-1,3-butadiene;

[0729]diisopropylamidoborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)hafniumη⁴-2,4-hexadiene;

[0730]diisopropylamidoborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)hafniumη⁴-1,4-dinaphthyl-1,3-butadiene;

[0731]diisopropylamidoborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)hafniumη⁴-¹-phenyl-1,3-pentadiene;

[0732]diisopropylamidoborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)hafniumnη⁴-1,3-pentadiene;

[0733]diisopropylamidoborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)hafniumdichloride;

[0734]diisopropylamidoborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)hafniumdimethyl;

[0735]diisopropylamidoborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)hafniumbis-dimethylamide;

[0736]diisopropylamidoborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)hafnium2-methyl-1,3-butadiene;

[0737]diisopropylamidoborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)hafnium2,3-dimethyl-1,3-butadiene;

[0738]diisopropylamidoborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)hafnium2-N,N-dimethylaminobenzyl;

[0739]diisopropylamidoborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)hafniumallyl;

[0740]diisopropylamidoborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)hafniumη⁴-1,4-diphenyl-1,3-butadiene;

[0741]diisopropylamidoborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)hafniumη⁴-2,4-hexadiene;

[0742]diisopropylamidoborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)hafniumη⁴-1,4-dinaphthyl-1,3-butadiene;

[0743]diisopropylamidoborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)hafniumη⁴-1-phenyl-1,3-pentadiene;.

[0744]diisopropylamidoborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)hafniumη⁴-1,3-pentadiene;

[0745] diisopropylamidoborane-bis-η⁵-(3-isopropylinden-1-yl)hafniumdichloride;

[0746] diisopropylamidoborane-bis-η⁵-(3-isopropylinden-1-yl)hafniumdimethyl;

[0747] diisopropylamidoborane-bis-η⁵-(3-isopropylinden-1-yl)hafniumbis-dimethylamide;

[0748] diisopropylamidoborane-bis-η⁵-(3-isopropylinden-1-yl)hafnium2-methyl-1,3-butadiene;

[0749] diisopropylamidoborane-bis-η⁵-(3-isopropylinden-1-yl)hafnium2,3-dimethyl-1,3-butadiene;

[0750] diisopropylamidoborane-bis-η⁵-(3-isopropylinden-1-yl)hafnium2-N,N-dimethylaminobenzyl;

[0751] diisopropylamidoborane-bis-η⁵-(3-isopropylinden-1-y)hafniumallyl;

[0752] diisopropylamidoborane-bis-η⁵-(3-isopropylinden-1-yl)hafniumallyl-1,4-diphenyl-1,3-butadiene;

[0753] diisopropylamidoborane-bis-η⁵-(3-isopropylinden-1-yl)hafniumη⁴-2,4-hexadiene;

[0754] diisopropylamidoborane-bis-η⁵-(3-isopropylinden-1-yl)hafniumη⁴-1,4-dinaphthyl-1,3-butadiene;

[0755] diisopropylamidoborane-bis-η⁵-(3-isopropylinden-1-yl)hafniumη⁴-1-phenyl-1,3-pentadiene;

[0756] diisopropylamidoborane-bis-η⁵-(3-isopropylinden-1-yl)hafniumη⁴-1,3-pentadiene;

[0757] diisopropylamidoborane-bis-η⁵-(3-t-butylinden-1-yl)hafniumdichloride;

[0758] diisopropylamidoborane-bis-η⁵-(3-t-butylinden-1-yl)hafniumdimethyl;

[0759] diisopropylamidoborane-bis-η⁵-(3-t-butylinden-1-yl)hafniumbis-dimethylamide;

[0760] diisopropylamidoborane-bis-η⁵-(3-t-butylinden-1-yl)hafnium2-methyl-1,3-butadiene;

[0761] diisopropylamidoborane-bis-η⁵-(3-t-butylinden-1-yl)hafnium2,3-dimethyl-1,3-butadiene;

[0762] diisopropylamidoborane-bis-η⁵-(3-t-butylinden-1-yl)hafnium2-N,N-dimethylaminobenzyl;

[0763] diisopropylamidoborane-bis-η⁵-(3-t-butylinden-1-yl)hafnium allyl;

[0764] diisopropylamidoborane-bis-η⁵-(3-t-butylinden-1-yl)hafniumη⁴-1,4-diphenyl-1,3-butadiene;

[0765] diisopropylamidoborane-bis-η⁵-(3-t-butylinden-1-yl)hafniumη⁴-2,4-hexadiene;

[0766] diisopropylamidoborane-bis-η⁵-(3-t-butylinden-1-yl)hafniumη⁴-1,4-dinaphthyl-1,3-butadiene;

[0767] diisopropylamidoborane-bis-η⁵-(3-t-butylinden-1-yl)hafniumη⁴-1-phenyl-1,3-pentadiene;

[0768] diisopropylamidoborane-bis-η⁵-(3-t-butylinden-1-yl)hafniumη⁴-1,3-pentadiene;

[0769] bis(trimethylsilyl)amidoborane-bis-η⁵-cyclopentadienylhafniumdichloride;

[0770] bis(trimethylsilyl)amidoborane-bis-η⁵-cyclopentadienylhafniumdimethyl;

[0771] bis(trimethylsilyl)amidoborane-bis-η⁵-cyclopentadienylhafniumbis-dimethylamide;

[0772] bis(trimethylsilyl)amidoborane-bis-η⁵-cyclopentadienylhafnium2-methyl-1,3-butadiene;

[0773] bis(trimethylsilyl)amidoborane-bis-η⁵-cyclopentadienylhafnium2,3-dimethyl-1,3-butadiene;

[0774] bis(trimethylsilyl)amidoborane-bis-η⁵-cyclopentadienylhafnium2-N,N-dimethylaminobenzyl;

[0775] bis(trimethylsilyl)amidoborane-bis-η⁵-cyclopentadienylhafniumallyl;

[0776] bis(trimethylsilyl)amidoborane-bis-η⁵-cyclopentadienylhafniumη⁴-1,4-diphenyl-1,3-butadiene;

[0777] bis(trimethylsilyl)amidoborane-bis-η⁵-cyclopentadienylhafniumη⁴-2,4-hexadiene;

[0778] bis(trimethylsilyl)amidoborane-bis-η⁵-cylopentadibhylhafniumη⁴-1,4-dinaphthyl-1,3-butadiene;

[0779] bis(trimethylsilyl)amidoborane-bis-η⁵-cyclopentadienylhafniumη⁴-1-phenyl-1,3-pentadiene;

[0780] bis(trimethylsilyl)amidoborane-bis-η⁵-cyclopentadienylhafniumη⁵-1,3-pentadiene;

[0781] bis(trimethylsilyl)amidoborane-bis-η⁵-inden-1-ylhafniumdichloride;

[0782] bis(trimethylsilyl)amidoborane-bis-η⁵-inden-1-ylhafnium dimethyl;

[0783] bis(trimethylsilyl)amidoborane-bis-η⁵-inden-1-ylhafniumbis-dimethylamide;

[0784] bis(trimethylsilyl)amidoborane-bis-η⁵-inden-1-ylhafnium2-methyl-1,3-butadiene;

[0785] bis(trimethylsilyl)amidoborane-bis-η⁵-inden-1-ylhafnium2,3-dimethyl-1,3-butadiene;

[0786] bis(trimethylsilyl)amidoborane-bis-η⁵-inden-1-ylhafnium2-N,N-dimethylaminobenzyl;

[0787] bis(trimethylsilyl)amidoborane-bis-η⁵-inden-1-ylhafnium allyl;

[0788] bis(trimethylsilyl)amidoborane-bis-η⁵-inden-1-ylhafniumη⁴-1,4-diphenyl-1,3-butadiene;

[0789] bis(trimethylsilyl)amidoborane-bis-η⁵-inden-1-ylhafniumη⁴-2,4-hexadiene;

[0790] bis(trimethylsilyl)amidoborane-bis-η⁵-inden-1-ylhafniumη⁴-1,4-dinaphthyl-1,3-butadiene;

[0791] bis(trimethylsilyl)amidoborane-bis-η⁵-inden-1-ylhafniumη⁴-1-phenyl-1,3-pentadiene;

[0792] bis(trimethylsilyl)amidoborane-bis-η⁵-inden-1-ylhafniumη⁴-1,3-pentadiene;

[0793] bis(trimethylsilyl)amidoborane-bis-η⁵-(2-methylinden-1-yl)hafniumdichloride;

[0794] bis(trimethylsilyl)amidoborane-bis-η⁵-(2-methylinden-1-yl)hafniumdimethyl;

[0795] bis(trimethylsilyl)amidoborane-bis-η⁵-(2-methylinden-1-ylhafniumbis-dimethylamide;

[0796] bis(trimethylsilyl)amidoborane-bis-η⁵-(2-methylinden-1-yl)hafnium2-methyl-1,3-butadiene;

[0797] bis(trimethylsilyl)amidoborane-bis-η⁵-(2-methylinden-1-yl)hafnium2,3-dimethyl-1,3-butadiene;

[0798] bis(trimethylsilyl)amidoborane-bis-η⁵-(2-methylinden-1-yl)hafnium2-N,N-dimethylaminobenzyl;

[0799] bis(trimethylsilyl)amidoborane-bis-η⁵-(2-methylinden-1-yl)hafniumallyl;

[0800] bis(trimethylsilyl)amidoborane-bis-η⁵-(2-methylinden-1-yl)hafniumη⁴-1,4-diphenyl-1,3-butadiene;

[0801] bis(trimethylsilyl)amidoborane-bis-η⁵-(2-methylinden-1-yl)hafniumη⁴-2,4-hexadiene;

[0802] bis(trimethylsilyl)amidoborane-bis-η⁵-(2-methylinden-1-yl)hafniumη⁴-1,4-dinaphthyl-1,3-butadiene;

[0803] bis(trimethylsilyl)amidoborane-bis-η⁵-(2-methylinden-1-yl)hafniumη⁴-1-phenyl-1,3-pentadiene;

[0804] bis(trimethylsilyl)amidoborane-bis-η⁵-(2-methylinden-1-yl)hafniumη⁴-1,3-pentadiene;

[0805]bis(trimethylsilyl)amidoborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)hafniumdichloride;

[0806]bis(trimethylsilyl)amidoborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)hafniumdimethyl;

[0807]bis(trimethylsilyl)amidoborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)hafniumbis-dimethylamide;

[0808]bis(trimethylsilyl)amidoborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)hafnium2-methyl-1,3-butadiene;

[0809]bis(trimethylsilyl)amidoborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)hafnium2,3-dimethyl-1,3-butadiene;

[0810]bis(trimethylsilyl)amidoborane-bis-η⁵-(2-methyl-4-phenylinden-1yl)hafnium2-N,N-dimethylaminobenzyl;

[0811]bis(trimethylsilyl)amidoborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)hafniumallyl;

[0812]bis(trimethylsilyl)amidoborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)hafniumη⁴-1,4-diphenyl-1,3-butadiene;

[0813]bis(trimethylsilyl)amidoborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)hafniumη⁴-2,4-hexadiene;

[0814]bis(trimethylsilyl)amidoborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)hafniumη⁴-1,4-dinaphthyl-1,3-butadiene;

[0815]bis(trimethylsilyl)amidoborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)hafniumη⁴-1-phenyl-1,3-pentadiene;

[0816]bis(trimethylsilyl)amidoborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)hafniumη⁴-1,3-pentadiene;

[0817]bis(trimethylsilyl)amidoborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)hafniumdichloride;

[0818]bis(trimethylsilyl)amidoborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)hafniumdimethyl;

[0819]bis(trimethylsilyl)amidoborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)hafniumbis-dimethylamide;

[0820]bis(trimethylsilyl)amidoborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)hafnium2-methyl-1,3-butadiene;

[0821]bis(trimethylsilyl)amidoborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)hafnium2,3-dimethyl-1,3-butadiene;

[0822]bis(trimethylsilyl)amidoborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)hafnium2-N,N-dimethylaminobenzyl;

[0823]bis(trimethylsilyl)amidoborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)hafniumallyl;

[0824]bis(trimethylsilyl)amidoborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)hafniumη⁴-1,4-diphenyl-1,3-butadiene;

[0825]bis(trimethylsilyl)amidoborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)hafniumη⁴-2,4-hexadiene;

[0826]bis(trimethylsilyl)amidoborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)hafniumη⁵-1,4-dinaphthyl-1,3-butadiene;

[0827]bis(trimethylsilyl)amidoborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)hafniumη⁴-1-phenyl-1,3-pentadiene;

[0828]bis(trimethylsilyl)amidoborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)hafniumη⁴-1,3-pentadiene;

[0829]bis(trimethylsilyl)amidoborane-bis-η⁵-(3-isopropylinden-1-yl)hafniumdichloride;

[0830]bis(trimethylsilyl)amidoborane-bis-η⁵-(3-isopropylinden-1-yl)hafniumdimethyl;

[0831]bis(trimethylsilyl)amidoborane-bis-η⁵-(3-isopropylinden-1-yl)hafniumbis-dimethylamide;

[0832]bis(trimethylsilyl)amidoborane-bis-η⁵-(3-isopropylinden-1-yl)hafnium2-methyl-1,3-butadiene;

[0833]bis(trimethylsilyl)amidoborane-bis-η⁵-(3-isopropylinden-1-yl)hafnium2,3-dimethyl-1,3-butadiene;

[0834]bis(trimethylsilyl)amidoborane-bis-η⁵-(3-isopropylinden-1-yl)hafnium2-N,N-dimethylaminobenzyl;

[0835]bis(trimethylsilyl)amidoborane-bis-η⁵-(3-isopropylinden-1-yl)hafniumallyl;

[0836]bis(trimethylsilyl)amidoborane-bis-η⁵-(3-isopropylinden-1-yl)hafniumη⁴-1,4-diphenyl-1,3-butadiene;

[0837]bis(trimethylsilyl)amidoborane-bis-η⁵-(3-isopropylinden-1-yl)hafniumη⁴-2,4-hexadiene;

[0838]bis(trimethylsilyl)amidoborane-bis-η⁵-(3-isopropylinden-1-yl)hafniumη⁴-1,4-dinaphthyl-1,3-butadiene;

[0839]bis(trimethylsilyl)amidoborane-bis-η⁵-(3-isopropylinden-1-yl)hafniumη⁴-1-phenyl-1,3-pentadiene;

[0840]bis(trimethylsilyl)amidoborane-bis-η⁵-(3-isopropylinden-1-yl)hafniumη⁴-1,3-pentadiene;

[0841]bis(trimethylsilyl)amidoborane-bis-η⁵-(3-t-butylinden-1-yl)hafniumdichloride;

[0842]bis(trimethylsilyl)amidoborane-bis-η⁵-(3-t-butylinden-1-yl)hafniumdimethyl;

[0843] bis(trimethylsilyl)amidoborane-bis-η⁵-(3-t-butylinden1-yl)hafniumbis-dimethylamide;

[0844]bis(trimethylsilyl)amidoborane-bis-η⁵-(3-t-butylinden-1-yl)hafnium2-methyl-1,3-butadiene;

[0845]bis(trimethylsilyl)amidoborane-bis-η⁵-(3-t-butylinden-1-yl)hafnium2,3-dimethyl-1,3-butadiene;

[0846]bis(trimethylsilyl)amidoborane-bis-η⁵-(3-t-butylinden-1-yl)hafnium2-N,N-dimethylaminobenzyl;

[0847]bis(trimethylsilyl)amidoborane-bis-η⁵-(3-t-butylinden-1-yl)hafniumallyl;

[0848]bis(trimethylsilyl)amidoborane-bis-η⁵-(3-t-butylinden-1-yl)hafniumη⁴-diphenyl-1,3-butadiene;

[0849]bis(trimethylsilyl)amidoborane-bis-η⁵-(3-t-butylinden-1-yl)hafniumη⁴-2,4-hexadiene;

[0850]bis(trimethylsilyl)amidoborane-bis-η⁵-(3-t-butylinden-1-yl)hafniumη⁴-1,4-dinaphthyl-1,3-butadiene;

[0851]bis(trimethylsilyl)amidoborane-bis-η⁵-(3-t-butylinden-1-yl)hafniumη⁴-1-phenyl-1,3-pentadiene;

[0852]bis(trimethylsilyl)amidoborane-bis-η⁵-(3-t-butylinden-1-yl)hafniumη⁴-1,3-pentadiene;

[0853]bis(diisopropylamido)diborane-1,2-bis-η⁵-(2-methyl-4-phenylinden-1-yl)hafniumdichloride;

[0854]bis(diisopropylamido)diborane-1,2-bis-η⁵-(2-methyl-4-phenylinden-1-yl)hafniumdimethyl;

[0855]bis(diisopropylamido)diborane-1,2-bis-η⁵-(2-methyl-4-phenylinden-1-yl)hafniumbis-dimethylamide;

[0856]bis(diisopropylamido)diborane-1,2-bis-η⁵-(2-methyl-4-phenylinden-1-yl)hafnium2-methyl-1,3-butadiene;

[0857]bis(diisopropylamido)diborane-1,2-bis-η⁵-(2-methyl-4-phenylinden-1-yl)hafnium2,3-dimethyl-1,3-butadiene;

[0858]bis(diisopropylamido)diborane-1,2-bis-η⁵-(2-methyl-4-phenylinden-1-yl)hafnium2-N,N-dimethylaminobenzyl;

[0859]bis(diisopropylamido)diborane-1,2-bis-η⁵-(2-methyl-4-phenylinden-1-yl)hafniumallyl;

[0860]bis(diisopropylamido)diborane-1,2-bis-η⁵-(2-methyl-4-phenylinden-1-yl)hafniumη⁴-1,4-diphenyl-1,3-butadiene;

[0861]bis(diisopropylamido)diborane-1,2-bis-η⁵-(2-methyl-4-phenylinden-1-yl)hafniumη⁴-2,4-hexadiene;

[0862]bis(diisopropylamido)diborane-1,2-bis-η⁵-(2-methyl-4-phenylinden-1-yl)hafniumη⁴-1,4-dinaphthyl-1,3-butadiene;

[0863]bis(diisopropylamido)diborane-1,2-bis-η⁵-(2-methyl-4-phenylinden-1-yl)hafniumη⁴-1-phenyl-1,3-pentadiene;

[0864]bis(diisopropylamido)diborane-1,2-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconiumη⁴-1,3-pentadiene;

[0865](η⁵-tetramethylcyclopentadienyl)(tert-butylamido)diisopropylamidoboranetitanium dichloride,

[0866](η⁵-tetramethylcyclopentadienyl)(tert-butylamido)diisopropylamidoboranetitanium dimethyl;

[0867](η⁵-tetramethylcyclopentadienyl)(tert-butylamido)diisopropylamidoboranetitanium bis-dimethylamide;

[0868](η⁵-tetramethylcyclopentadienyl)(tert-butylamido)diisopropylamidoboranetitanium 2-methyl-1,3-butadiene;

[0869](η⁵-tetramethylcyclopentadienyl)(tert-butylamido)diisopropylamidoboranetitanium 2,3-dimethyl-1,3-butadiene;

[0870](η⁵-tetramethylcyclopentadienyl)(tert-butylamido)diisopropylamidoboranetitanium 2-N,N-dimethylaminobenzyl;

[0871](η⁵-tetramethylcyclopentadienyl)(tert-butylamido)diisopropylamidoboranetitanium allyl;

[0872](η⁵-tetramethylcyclopentadienyl)(tert-butylamido)diisopropylamidoboranetitanium η⁴-1,4-diphenyl-1,3-butadiene;

[0873](η⁵-tetramethylcyclopentadienyl)(tert-butylamido)diisopropylamidoboranetitanium η⁴-2,4-hexadiene;

[0874](η⁵-tetramethylcyclopentadienyl)(tert-butylamido)diisopropylamidoboranetitanium η⁴-dinaphthyl-1,3-butadiene;

[0875](η⁵-tetramethylcyclopentadienyl)(tert-butylamido)diisopropylamidoboranetitanium η⁴-1,3-pentadiene;

[0876](η⁵-tetramethylcyclopentadienyl)(tert-butylamido)diisopropylamidoboranetitanium η⁴-1,3-pentadiene;

[0877](η⁵-tetramethylcyclopentadienyl)(tert-butylamido)diisopropylamidoboranetitanium dichloride;

[0878](η⁵-tetramethylcyclopentadienyl)(cyclohexylamido)diisopropylamidoboranetitanium dimethyl;

[0879](η⁵-tetramethylcyclopentadienyl)(cyclohexylamido)diisopropylamidoboranetitanium bis-dimethylamide;

[0880](η⁵-tetramethylcyclopentadienyl)(cyclohexylamido)diisopropylamidoboranetitanium 2-methyl-1,3-butadiene;

[0881](η⁵-tetramethylcyclopentadienyl)(cyclohexylamido)diisopropylamidoboranetitanium 2,3-dimethyl-1,3-butadiene;

[0882](η⁵-tetramethylcyclopentadienyl)(cyclohexylamido)diisopropylamidoboranetitanium 2-N,N-dimethylaminobenzyl;

[0883](η⁵-tetramethylcyclopentadienyl)(cyclohexylamido)diisopropylamidoboranetitanium allyl;

[0884](η⁵-tetramethylcyclopentadienyl)(cyclohexylamido)diisopropylamidoboranetitanium η⁴-1,4-diphenyl-1,3-butadiene;

[0885](η⁵-tetramethylcyclopentadienyl)(cyclohexylamido)diisopropylamidoboranetitanium η⁵-2,4-hexadiene;

[0886](η⁵-tetramethylcyclopentadienyl)(cyclohexylamido)diisopropylamidoboranetitanium η⁴-1,4-dinaphthyl-1,3-butadiene;.

[0887](η⁵-tetramethylcyclopentadienyl)(cyclohexylamido)diisopropylamidoboranetitanium η⁴-1-phenyl-1,3-pentadiene;

[0888](η⁵-tetramethylcyclopentadienyl)(cyclohexylamido)diisopropylamidoboranetitanium η⁴-1,3-pentadiene;

[0889] (η⁵-tetramethylcyclopentadienyl)(tert-butylamido)bis(diisopropylamide) diborane titanium dichloride;

[0890] (η⁵-tetramethylcyclopentadienyl)(tert-butylamido)bis(diisopropylamide) diborane titanium dimethyl;

[0891] (η⁵-tetramethylcyclopentadienyl)(tert-butylamido)bis(diisopropylamide) diborane titanium bis-dimethylamide;

[0892] (η⁵-tetramethylcyclopentadienyl)(tert-butylamido)bis(diisopropylamide) diborane titanium 2-methyl-1,3-butadiene;

[0893] (η⁵-tetramethylcyclopentadienyl)(tert-butylamido)bis(diisopropylamide) diborane titanium 2,3-dimethyl-1,3-butadiene;

[0894] (η⁵-tetramethylcyclopentadienyl)(tert-butylamido)bis(diisopropylamide). diborane titanium 2-N,N-dimethylaminobenzyl;

[0895] (η⁵-tetramethylcyclopentadienyl)(tert-butylamido)bis(diisopropylamide) diborane titanium allyl;

[0896] (η⁵-tetramethylcyclopentadienyl)(tert-butylamido)bis(diisopropylamide) diborane titanium η⁴-1,4-diphenyl-1,3-butadiene;

[0897] (η⁵-tetramethylcyclopentadienyl)(tert-butylamido)bis(diisopropylamide) diborane titanium η⁴-2,4-hexadiene;

[0898] (η⁵-tetramethylcyclopentadienyl)(tert-butylamido)bis(diisopropylamide) diborane titanium η⁴-1,4-dinaphthyl-1,3-butadiene;

[0899] (η⁵-tetramethylcyclopentadienyl)(tert-butylamido)bis(diisopropylamide) diborane titanium η⁴-1-phenyl-1,3-pentadiene;

[0900] (η⁵-tetramethylcyclopentadienyl)(tert-butylamido)bis(diisopropylamide) diborane titanium η⁴-1,3-pentadiene;

[0901](η⁵-tetramethylcyclopentadienyl)(phenylamido)diisopropylamidoboranetitanium dichloride;

[0902](η⁵-tetramethylcyclopentadienyl)(phenylamido)diisopropylamidoboranetitanium dimethyl;

[0903](η⁵-tetramethylcyclopentadienyl)(phenylamido)diisopropylamidoboranetitanium bis-dimethylamide;

[0904](η⁵-tetramethylcyclopentadienyl)(phenylamido)diisopropylamidoboranetitanium 2-methyl-1,3-butadiene;

[0905](η⁵-tetramethylcyclopentadienyl)(phenylamido)diisopropylamidoboranetitanium 2,3-dimethyl-1,3-butadiene;

[0906](η⁵-tetramethylcyclopentadienyl)(phenylamido)diisopropylamidoboranetitanium 2-N,N-dimethylaminobenzyl;

[0907](η⁵-tetramethylcyclopentadienyl)(phenylamido)diisopropylamidoboranetitanium allyl;

[0908](η⁵-tetramethylcyclopentadienyl)(phenylamido)diisopropylamidoboranetitanium η⁴-1,4-diphenyl-1,3-butadiene;

[0909](η⁵-tetramethylcyclopentadienyl)(phenylamido)diisopropylamidoboranetitanium η⁴-2,4-hexadiene;

[0910](η⁵-tetramethylcyclopentadienyl)(phenylamido)diisopropylamidoboranetitanium η⁴-1,4-dinaphthyl-1,3-butadiene;

[0911](η⁵-tetramethylcyclopentadienyl)(phenylamido)diisopropylamidoboranetitanium η⁴-1-phenyl-1,3-pentadiene;

[0912](η⁵-tetramethylcyclopentadienyl)(phenylamido)diisopropylamidoboranetitanium η⁴-1,3-pentadiene;

[0913] (η⁵-tetramethylcyclopentadienyl)(tert-butylamido)dimethylamidoborane titanium dichloride;

[0914] (η⁵-tetramethylcyclopentadienyl)(tert-butylamido)dimethylamidoborane titanium dimethyl;

[0915] (η⁵-tetramethylcyclopentadienyl)(tert-butylamido)dimethylamidoborane titanium bis-dimethylamide;

[0916] (η⁵-tetramethylcyclopentadienyl)(tert-butylamido)dimethylamidoborane titanium 2-methyl-1,3-butadiene;

[0917] (η⁵-tetramethylcyclopentadienyl)(tert-butylamido)dimethylamidoborane titanium 2,3-dimethyl-1,3-butadiene;

[0918] (η⁵-tetramethylcyclopentadienyl)(tert-butylamido)dimethylamidoborane titanium 2-N,N-dimethylaminobenzyl;

[0919] (η⁵-tetramethylcyclopentadienyl)(tert-butylamido)dimethylamidoborane titanium allyl;

[0920] (η⁵-tetramethylcyclopentadienyl)(tert-butylamido)dimethylamidoborane titanium η⁴-1,4-diphenyl-1,3-butadiene;

[0921] (η⁵-tetramethylcyclopentadienyl)(tert-butylamido)dimethylamidoborane titanium η⁴-2,4-hexadiene;

[0922] (η⁵-tetramethylcyclopentadienyl)(tert-butylamido)dimethylamidoborane titanium η⁴-1,4-dinaphthyl-1,3-butadiene;

[0923] (η⁵-tetramethylcyclopentadienyl)(tert-butylamido)dimethylamidoborane titanium η⁴-1-phenyl-1,3-pentadiene;

[0924] (η⁵-tetramethylcyclopentadienyl)(tert-butylamido)dimethylamidoborane titanium η⁴-1,3-pentadiene;

[0925] (η⁵-inden-1-yl)(tert-butylamido)diisopropylamidoborane titaniumdichloride;

[0926] (η⁵-inden-1-yl)(tert-butylamido)diisopropylamidoborane titaniumdimethyl;

[0927] (η⁵-inden-1-yl)(tert-butylamido)diisopropylamidoborane titaniumbis-dimethylamide;

[0928] (η⁵-inden-1-yl)(tert-butylamido)diisopropylamidoborane titanium2-methyl-1,3-butadiene;

[0929] (η⁵-inden-1-yl)(tert-butylamido)diisopropylamidoborane titanium2,3-dimethyl-1,3-butadiene;

[0930] (η⁵-inden-1-yl)(tert-butylamido)diisopropylamidoborane titanium2-N,N-dimethylaminobenzyl;

[0931] (η⁵-inden-1-yl)(tert-butylamido)diisopropylamidoborane titaniumallyl,

[0932] (η⁵-inden-1-yl)(tert-butylamido)diisopropylamidoborane titaniumη⁴-1,4-diphenyl-1,3-butadiene;

[0933] (η⁵-inden-1-yl)(tert-butylamido)diisopropylamidoborane titaniumη⁴-2,4-hexadiene;

[0934] (η⁵-inden-1-yl)(tert-butylamido)diisopropylamidoborane titaniumη⁴-dinaphthyl-1,3-butadiene;

[0935] (η⁵-inden-1-yl)(tert-butylamido)diisopropylamidoborane titaniumη⁴-1-phenyl-1,3-pentadiene;

[0936] (η⁵-inden-1-yl)(tert-butylamido)diisopropylamidoborane titaniumη⁴-1,3-pentadiene;

[0937] (η⁵-2,3-dimethyl-1-)(tert-butylamido)diisopropylamidoboranetitanium dichloride;

[0938](η⁵-2,3-dimethylinden-1-yl)(tert-butylamido)diisopropylamidoboranetitanium dimethyl;

[0939](η⁵-2,3-dimethylinden-1-yl)(tert-butylamido)diisopropylamidoboranetitanium bis-dimethylamide;

[0940](η⁵-2,3-dimethylinden-1-yl)(tert-butylamido)diisopropylamidoboranetitanium 2-methyl-1,3-butadiene;

[0941](η⁵-2,3-dimethylinden-1-yl)(tert-butylamido)diisopropylamidoboranetitanium 2,3-dimethyl-1,3-butadiene;

[0942](η⁵-2,3-dimethylinden-1-yl)(tert-butylamido)diisopropylamidoboranetitanium 2-N,N-dimethylaminobenzyl;

[0943](η⁵-2,3-dimethylinden-1-yl)(tert-butylamido)diisopropylamidoboranetitanium allyl;

[0944](η⁵-2,3-dimethylinden-1-yl)(tert-butylamido)diisopropylamidoboranetitanium η⁴-1,4-diphenyl-1,3-butadiene;

[0945](η⁵-2,3-dimethylinden-1-yl)(tert-butylamido)diisopropylamidoboranetitanium η⁴-2,4-hexadiene;

[0946](η⁵-2,3-dimethylinden-1-yl)(tert-butylamido)diisopropylamidoboranetitanium η⁴-1,4-dinaphthyl-1,3-butadiene;

[0947](η⁵-2,3-dimethylinden-1-yl)(tert-butylamido)diisopropylamidoboranetitanium η⁴-1-phenyl-1,3-pentadiene;

[0948](η⁵-2,3-dimethylinden-1-yl)(tert-butylamido)diisopropylamidoboranetitanium η⁴-1,3-pentadiene;

[0949](η⁵-2-pyrrolidenylinden-1-yl)(tert-butylamido)diisopropylamidoboranetitanium dichloride;

[0950](η⁵-2-pyrrolidenylinden-1-yl)(tert-butylamido)diisopropylamidoboranetitanium dimethyl;

[0951](η⁵-2-pyrrolidenylinden-1-yl)(tert-butylamido)diisopropylamidoboranetitanium bis-dimethylamide;

[0952](η⁵-2-pyrrolidenylinden-1-yl)(tert-butylamido)diisopropylamidoboranetitanium 2-methyl-1,3-butadiene;

[0953](η⁵-2-pyrrolidenylinden-1-yl)(tert-butylamido)diisopropylamidoboranetitanium 2,3-dimethyl-1,3-butadiene;

[0954](η⁵-2-pyrrolidenylinden-1-yl)(tert-butylamido)diisopropylamidoboranetitanium 2-N,N-dimethylaminobenzyl;

[0955](η⁵-2-pyrrolidenylinden-1-yl)(tert-butylamido)diisopropylamidoboranetitanium allyl;

[0956](η⁵-2-pyrrolidenylinden-1-yl)(tert-butylamido)diisopropylamidoboranetitanium η⁴-1,4-diphenyl-1,3-butadiene;

[0957](η⁵-2-pyrrolidenylinden-1-yl)(tert-butylamido)diisopropylamidoboranetitanium η⁴-2,4-hexadiene;

[0958](η⁵-2-pyrrolidenylinden-1-y)(tert-butylamido)diisopropylamidoboranetitanium η⁴-1,4-dinaphthyl-1,3-butadiene;

[0959](η⁵-2-pyrrolidenylinden-1-yl)(tert-butylamido)diisopropylamidoboranetitanium η⁴-1-phenyl-1,3-pentadiene;

[0960](η⁵-2-pyrrolidenylinden-1-yl)(tert-butylamido)diisopropylamidoboranetitanium η⁴-1,3-pentadiene;bis-phenylamido-bis(diisopropylamido)diborane titanium dichloride;

[0961] bis-phenylamido-bis(diisopropylamido)diborane titanium dimethyl;

[0962] bis-phenylamido-bis(diisopropylamido)diborane titaniumbis-dimethylamide;

[0963] bis-phenylamido-bis(diisopropylamido)diborane titanium2-methyl-1,3-butadiene;

[0964] bis-phenylamido-bis(diisopropylamido)diborane titanium2,3dimethyl-1,3-butadiene;

[0965] bis-phenylamido-bis(diisopropylamido)diborane titanium2-N,N-dimethylaminobenzyl;

[0966] bis-phenylamido-bis(diisopropylamido)diborane titanium allyl;

[0967] bis-phenylamido-bis(diisopropylamido)diborane titaniumη⁴-1,4-diphenyl-1,3-butadiene;

[0968] bis-phenylamido-bis(diisopropylamido)diborane titaniumη⁴-2,4-hexadiene;

[0969] bis-phenylamido-bis(diisopropylamido)diborane titaniumη⁴-1,4-dinaphthyl-1,3-butadiene;

[0970] bis-phenylamido-bis(diisopropylamido)diborane titaniumη⁴-1-phenyl-1,3-pentadiene;

[0971] bis-phenylamido-bis(diisopropylamido)diborane titaniumη⁴-1,3-pentadiene;

[0972] bis-2,6-diisopropylphenylamido-bis(diisopropylamido)diboranetitanium dichloride;

[0973] bis-2,6-diisopropylphenylamido-bis(diisopropylamido)diboranetitanium dimethyl;

[0974] bis-2,6-diisopropylphenylamido-bis(diisopropylamido)diboranetitanium bis-dimethylamide;

[0975] bis-2,6-diisopropylphenylamido-bis(diisopropylamido)diboranetitanium 2-methyl-1,3-butadiene;

[0976] bis-2,6-diisopropylphenylamido-bis(diisopropylamido)diboranetitanium 2,3-dimethyl-1,3-butadiene;

[0977] bis-2,6-diisopropylphenylamido-bis(diisopropylamido)diboranetitanium 2-N,N-dimethylaminobenzyl;

[0978] bis-2,6-diisopropylphenylamido-bis(diisopropylamido)diboranetitanium allyl;

[0979] bis-2,6-diisopropylphenylamido-bis(diisopropylamido)diboranetitanium η⁴-1,4-diphenyl-1,3-butadiene;

[0980] bis-2,6-diisopropylphenylamido-bis(diisopropylamido)diboranetitanium η⁴-2,4-hexadiene;

[0981] bis-2,6-diisopropylphenylamido-bis(diisopropylamido)diboranetitanium η⁴-1,4-dinaphthyl-1,3-butadiene;

[0982] bis-2,6-diisopropylphenylamido-bis(diisopropylamido)diboranetitanium η⁴-1-phenyl-1,3-pentadiene;

[0983] bis-2,6-diisopropylphenylamido-bis(diisopropylamido)diboranetitanium η⁴-1,3-pentadiene;

[0984] bis-3,5-dimethylbenzylamido-bis(dimethylamido)diborane titaniumdichloride;

[0985] bis-3,5-dimethylbenzylamido-bis(dimethylamido)diborane titaniumdimethyl;

[0986] bis-3,5-dimethylbenzylamido-bis(dimethylamido)diborane titaniumbis-dimethylamide;

[0987] bis-3,5-dimethylbenzylamido-bis(dimethylamido)diborane titanium2-methyl-1,3-butadiene;

[0988] bis-3,5-dimethylbenzylamido-bis(dimethylamido)diborane titanium2,3-dimethyl-1,3-butadiene;

[0989] bis-3,5-dimethylbenzylamido-bis(dimethylamido)diborane titanium2-N,N-dimethylaminobenzyl;

[0990] bis-3,5-dimethylbenzylamido-bis(dimethylamido)diborane titaniumallyl;

[0991] bis-3,5-dimethylbenzylamido-bis(dimethylamido)diborane titaniumη⁴-1,4-diphenyl-1,3-butadiene;

[0992] bis-3,5-dimethylbenzylamido-bis(dimethylamido)diborane titaniumη⁴-2,4-hexadiene;

[0993] bis-3,5-dimethylbenzylamido-bis(dimethylamido)diborane titaniumη⁴-1,4-dinaphthyl-1,3-butadiene;

[0994] bis-3,5-dimethylbenzylamido-bis(dimethylamido)diborane titaniumη⁴-1-phenyl-1,3-pentadiene;

[0995] bis-3,5-dimethylbenzylamido-bis(dimethylamido)diborane titaniumη⁴-1,3-pentadiene;

[0996] bis-2,6-dimethylbenzylamido-bis(dimethylamido)diborane titaniumdichloride;

[0997] bis-2,6-dimethylbenzylamido-bis(dimethylamido)diborane titaniumdimethyl;

[0998] bis-2,6-dimethylbenzylamido-bis(dimethylamido)diborane titaniumbis-dimethylamide;

[0999] bis-2,6-dimethylbenzylamido-bis(dimethylamido)diborane-titanium2-methyl-1,3-butadiene;

[1000] bis-2,6-dimethylbenzylamido-bis(dimethylamido)diborane titanium2,3-dimethyl-1,3-butadiene;

[1001] bis-2,6-dimethylbenzylamido-bis(dimethylamido)diborane titanium2-N,N-dimethylaminobenzyl;

[1002] bis-2,6-dimethylbenzylamido-bis(dimethylamido)diborane titaniumallyl;

[1003] bis-2,6-dimethylbenzylamidobis(dimethylamido)diborane titaniumη⁴-1,4-diphenyl-1,3-butadiene;

[1004] bis-2,6-dimethylbenzylamido-bis(dimethylamido)diborane titaniumη⁴-2,4-hexadiene;

[1005] bis-2,6-dimethylbenzylamido-bis(dimethylamido)diborane titaniumη⁴-1,4-dinaphthyl-1,3-butadiene;

[1006] bis-2,6-dimethylbenzylamido-bis(dimethylamido)diborane titaniumη⁴-1-phenyl-1,3-pentadiene;

[1007] bis-2,6-dimethylbenzylamido-bis(dimethylamido)diborane titaniumη⁴-1,3-pentadiene;

[1008] bis-2,6-diisopropylphenylamido-bis(dimethylamido)diboranetitanium dichloride;

[1009] bis-2,6-diisopropylphenylamido-bis(dimethylamido)diboranetitanium dimethyl;

[1010] bis-2,6-diisopropylphenylamido-bis(dimethylamido)diboranetitanium bis-dimethylamide;

[1011] bis-2,6-diisopropylphenylamido-bis(dimethylamido)diboranetitanium 2-methyl-1,3-butadiene;

[1012] bis-2,6-diisopropylphenylamido-bis(dimethylamido)diboranetitanium 2,3-dimethyl-1,3-butadiene;

[1013] bis-2,6-diisopropylphenylamido-bis(dimethylamido)diboranetitanium 2-N,N-dimethylaminobenzyl;

[1014] bis-2,6-diisopropylphenylamido-bis(dimethylamido)diboranetitanium allyl;

[1015] bis-2,6-diisopropylphenylamido-bis(dimethylamido)diboranetitanium η⁴-diphenyl-1,3-butadiene;

[1016] bis-2,6-diisopropylphenylamido-bis(dimethylamido)diboranetitanium η⁴-2,4-hexadiene;

[1017] bis-2,6-diisopropylphenylamido-bis(dimethylamido)diboranetitanium η⁴-1 4-dinaphthyl-1,3-butadiene;

[1018]bis-2,6-diisopropylphenylamido-bis(dimethylamido)diborane-titaniumη⁴-1-phenyl-1,3-pentadiene;

[1019] bis-2,6-diisopropylphenylamido-bis(dimethylamido)diboranetitanium η³-pentadiene;

[1020]bis-2,6-diisopropylphenylamido-bis(bis(trimethylsilyl)amido)diboranetitanium dichloride;

[1021]bis-2,6-diisopropylphenylamido-bis(bis(trimethylsilyl)amido)diboranetitanium dimethyl;

[1022]bis-2,6-diisopropylphenylamido-bis(bis(trimethylsilyl)amido)diboranetitanium bis-dimethylamide;

[1023]bis-2,6-diisopropylphenylamido-bis(bis(trimethylsilyl)amido)diboranetitanium 2-methyl-1,3-butadiene;

[1024]bis-2,6-diisopropylphenylamido-bis(bis(trimethylsilyl)amido)diboranetitanium 2,3-dimethyl-1,3-butadiene;

[1025]bis-2,6-diisopropylphenylamido-bis(bis(trimethylsilyl)amido)diboranetitanium 2-N,N-dimethylaminobenzyl;

[1026]bis-2,6-diisopropylphenylamido-bis(bis(trimethylsilyl)amido)diboranetitanium allyl;

[1027]bis-2,6-diisopropylphenylamido-bis(bis(trimethylsilyl)amido)diboranetitanium η⁴-1,4-diphenyl-1,3-butadiene;

[1028]bis-2,6-diisopropylphenylamido-bis(bis(trimethylsilyl)amido)diboranetitanium η⁴-2,4-hexadiene;

[1029]bis-2,6-diisopropylphenylamido-bis(bis(trimethylsilyl)amido)diboranetitanium η⁴-1,4-dinaphthyl-1,3-butadiene;

[1030]bis-2,6-diisopropylphenylamido-bis(bis(trimethylsilyl)amido)diboranetitanium η⁴-1-phenyl-1,3-pentadiene;

[1031]bis-2,6-diisopropylphenylamido-bis(bis(trimethylsilyl)amido)diboranetitanium η⁴-1,3-pentadiene;

[1032] bis-2,6-diisopropylphenylamido-bis(diisopropylamido)diboranezirconium dichloride;

[1033] bis-2,6-diisopropylphenylamido-bis(diisopropylamido)diboranezirconium dimethyl;

[1034] bis-2,6diisopropylphenylamido-bis(diisopropylamido)diboranezirconium bis-dimethylamide;

[1035] bis-2,6-diisopropylphenylamido-bis(diisopropylamido)diboranezirconium 2-methyl-1,3-butadiene;

[1036] bis-2,6-diisopropylphenylamido-bis(diisopropylamido)diboranezirconium 2,3-dimethyl-1,3-butadiene;

[1037] bis-2,6-diisopropylphenylamido-bis(diisopropylamido)diboranezirconium 2-N,N-dimethylaminobenzyl;

[1038] bis-2,6-diisopropylphenylamido-bis(diisopropylamido)diboranezirconium allyl;

[1039] bis-2,6-diisopropylphenylamido-bis(diisopropylamido)diboranezirconium η⁴-1,4-diphenyl-1,3-butadiene;

[1040] bis-2,6-diisopropylphenylamido-bis(diisopropylamido)diboranezirconium ⁴-2,4-hexadiene;

[1041] bis-2,6-diisopropylphenylamido-bis(diisopropylamido)diboranezirconium η⁴-1,4-dinaphthyl-1,3-butadiene;

[1042] bis-2,6-diisopropylphenylamido-bis(diisopropylamido)diboranezirconium η⁴-1-phenyl-1,3-pentadiene;

[1043] bis-2,6-diisopropylphenylamido-bis(diisopropylamido)diboranezirconium η⁴-1,3-pentadiene;

[1044] bis-2-tert-butylphenylamido-bis(diisopropylamido)diboranetitanium dichloride;

[1045] bis-2-tert-butylphenylamido-bis(diisopropylamido)diboranetitanium dimethyl;

[1046] bis-2-tert-butylphenylamido-bis(diisopropylamido)diboranetitanium bis-dimethylamide;

[1047] bis-2-tert-butylphenylamido-bis(diisopropylamido)diboranetitanium 2-methyl-1,3-butadiene;

[1048] bis-2-tert-butylphenylamido-bis(diisopropylamido)diboranetitanium 2,3-dimethyl-1,3-butadiene;

[1049] bis-2-tent-butylphenylamido-bis(diisopropylamido)diboranetitanium 2-N,N-dimethylaminobenzyl;

[1050] bis-2-tert-butylphenylamido-bis(diisopropylamido)diboranetitanium allyl;

[1051] bis-2-tert-butylphenylamido-bis(diisopropylamido)diboranetitanium η⁴-1,4-diphenyl-1,3-butadiene;

[1052] bis-2-tert-butylphenylamido-bis(diisopropylamido)diboranetitanium η⁴-2,4-hexadiene;

[1053] bis-2-tert-butylphenylamido-bis(diisopropylamido)diboranetitanium η⁴-1,4-dinaphthyl-1,3-butadiene;

[1054] bis-2-tert-butylphenylamido-bis(diisopropylamido)diboranetitanium η⁴-1-phenyl-1,3-pentadiene; and

[1055] bis-2-tert-butylphenylamido-bis(diisopropylamido)diboranetitanium η⁴-1,3-pentadiene.

[1056] A further preferred class of Group 4 transition metal complexesof the present invention are represented in previously defined formulas4-9 wherein T is:

[1057] including such structures where two R¹ groups and R⁵ are linkedsuch as in 1,3,4,6,7,8, hexahydro-pyrimido[1,2-a] pyrimidinate, shownbelow:

[1058] In the foregoing species, it is believed, without wishing to bebound by such belief, that the ligand group, T, is connected to Z viathe heteroatoms thereof.

[1059] Specific, but not limiting, examples of the foregoing metalcomplexes included within the invention are:

[1060] N,N′-diisopropyl-phenyl-amidinateborane-bis-η⁵-cyclopentadienylzirconium dichloride;

[1061] N,N′-diisopropyl-phenyl-amidinateborane-bis-η⁵-cyclopentadienylzirconium dimethyl;

[1062] N,N′-diisopropyl-phenyl-amidinateborane-bis-η⁵-cyclopentadienylzirconium bis-dimethylamide;

[1063] N,N′-diisopropyl-phenyl-amidinateborane-bis-η⁵-cyclopentadienylzirconium 2-methyl-1,3-butadiene;

[1064] N,N′-diisopropyl-phenyl-amidinateborane-bis-η⁵-cyclopentadienylzirconium 2,3-dimethyl-1,3-butadiene;

[1065] N,N′-diisopropyl-phenyl-amidinateborane-bis-η⁵-cyclopentadienylzirconium 2-N,N-dimethylaminobenzyl;

[1066] N,N′-diisopropyl-phenyl-amidinateborane-bis-η⁵-cyclopentadienylzirconium allyl;

[1067] N,N′-diisopropyl-phenyl-amidinateborane-bis-η⁵-cyclopentadienylzirconium η⁴-1,4-diphenyl-1,3-butadiene;

[1068] N,N′-diisopropyl-phenyl-amidinateborane-bis-η⁵-cyclopentadienylzirconium η⁴-2,4-hexadiene;

[1069] N,N′-diisopropyl-phenyl-amidinateborane-bis-η⁵-cyclopentadienylzirconium η⁴-1,4-dinaphthyl-1,3-butadiene;

[1070] N,N′-diisopropyl-phenyl-amidinateborane-bis-η⁵-cyclopentadienylzirconium η⁴-1-phenyl-1,3-pentadiene;

[1071] N,N′-diisopropyl-phenyl-amidinateborane-bis-η⁵-cyclopentadienylzirconium ⁴-1,3-pentadiene;

[1072] N,N′-diisopropyl-3-phenyl-1,3-diketimineborane-bis-η⁵-cyclopentadienylzirconium dichloride;

[1073] N,N′-diisopropyl-3-phenyl-1,3-diketimineborane-bis-η⁵-cyclopentadienylzirconium dimethyl;

[1074] N,N′-diisopropyl-3-phenyl-1,3-diketimineborane-bis-η⁵-cyclopentadienylzirconium bis-dimethylamide;

[1075] N,N′-diisopropyl-3-phenyl-1,3-diketimineborane-bis-η⁵-cyclopentadienylzirconium 2-methyl-1,3-butadiene;

[1076] N,N′-diisopropyl-3-phenyl-1,3-diketimineborane-bis-η⁵-cyclopentadienylzirconium 2,3-dimethyl-1,3-butadiene;

[1077] N,N′-diisopropyl-3-phenyl-1,3-diketimineborane-bis-η⁵-cyclopentadienylzirconium 2-N,N-dimethylaminobenzyl;

[1078] N,N′-diisopropyl-3-phenyl-1,3-diketimineborane-bis-η⁵-cyclopentadienylzirconium allyl;

[1079] N,N′-diisopropyl-3-phenyl-1,3-diketimineborane-bis-η⁵-cyclopentadienylzirconium η⁴-1,4-diphenyl-1,3-butadiene;

[1080] N,N′-diisopropyl-3-phenyl-1,3-diketimineborane-bis-η⁵-cyclopentadienylzirconium η⁴-2,4-hexadiene;

[1081] N,N′-diisopropyl-3-phenyl-1,3-diketimineborane-bis-η⁵-cyclopentadienylzirconium η⁴-1,4-dinaphthyl-1,3-butadiene;

[1082] N,N′-diisopropyl-3-phenyl-1,3-diketimineborane-bis-η⁵-cyclopentadienylzirconium η⁴-1-phenyl-1,3-pentadiene;

[1083] N,N′-diisopropyl-3-phenyl-1,3-diketimineborane-bis-η⁵-cyclopentadienylzirconium η⁴-1,3-pentadiene;

[1084] N,N′-diisopropyl-dimethylguanidinateborane-bis-η⁵-cyclopentadienylzirconium dichloride;

[1085] N,N′-diisopropyl-dimethylguanidinateborane-bis-η⁵-cyclopentadienylzirconium dimethyl;

[1086] N,N′-diisopropyl-dimethylguanidinateborane-bis-η⁵-cyclopentadienylzirconium bis-dimethylamide;

[1087] N,N′-diisopropyl-dimethylguanidinateborane-bis-η⁵-cyclopentadienylzirconium 2-methyl-1,3-butadiene;

[1088] N,N′-diisopropyl-dimethylguanidinateborane-bis-η⁵-cyclopentadienylzirconium 2,3-dimethyl-1,3-butadiene;

[1089] N,N′-diisopropyl-dimethylguanidinateborane-bis-η⁵-cyclopentadienylzirconium 2-N,N-dimethylaminobenzyl;

[1090] N,N′-diisopropyl-dimethylguanidinateborane-bis-η⁵-cyclopentadienylzirconium allyl;

[1091] N,N′-diisopropyl-dimethylguanidinateborane-bis-η⁵-cyclopentadienylzirconium η⁴-1,4-diphenyl-1,3-butadiene;

[1092] N,N′-diisopropyl-dimethylguanidinateborane-bis-η⁵-cyclopentadienylzirconium η⁴-2,4-hexadiene;

[1093] N,N′-diisopropyl-dimethylguanidinateborane-bis-η⁵-cyclopentadienylzirconium η⁴-1,4-dinaphthyl-1,3-butadiene;

[1094] N,N′-diisopropyl-dimethylguanidinateborane-bis-η⁵-cyclopentadienylzirconium η⁴-1-phenyl-1,3-pentadiene;

[1095] N,N′-diisopropyl-dimethylguanidinateborane-bis-η⁵-cyclopentadienylzirconium η⁴-1,3-pentadiene;

[1096] 1,3,4,6,7,8-hexahydro-pyrimido[1,2-a] pyrimidinateborane-bis-η⁵-inden-1-ylzirconium dichloride;

[1097] 1,3,4,6,7,8-hexahydro-pyrimido[1,2-a] pyrimidinateborane-bis-η⁵-inden-1-ylzirconium dimethyl;

[1098] 1,3,4,6,7,8-hexahydro-pyrimido[1,2-a] pyrimidinateborane-bis-η⁵-inden-1-ylzirconium bis-dimethylamide;

[1099] 1,3,4,6,7,8-hexahydro-pyrimido[1,2-a] pyrimidinateborane-bis-η⁵-inden-1-ylzirconium 2-methyl-1,3-butadiene;

[1100] 1,3,4,6,7,8-hexahydro-pyrimido[1,2-a] pyrimidinateborane-bis-η⁵-inden-1-ylzirconium 2,3-dimethyl-1,3-butadiene;

[1101] 1,3,4,6,7,8-hexahydro-pyrimido[1,2-a] pyrimidinateborane-bis-η⁵-inden-1-ylzirconium 2-N,N-dimethylaminobenzyl;

[1102] 1,3,4,6,7,8-hexahydro-pyrimido[1,2-a] pyrimidinateborane-bis-η⁵-inden-1-ylzirconium allyl;

[1103] 1,3,4,6,7,8-hexahydro-pyrimido[1,2-a] pyrimidinateborane-bis-η⁵-inden-1-ylzirconium η⁴-1,4-diphenyl-1,3-butadiene;

[1104] 1,3,4,6,7,8-hexahydro-pyrimido[1,2-a] pyrimidinateborane-bis-η⁵-inden-1-ylzirconium η⁴-2,4-hexadiene;

[1105] 1,3,4,6,7,8-hexahydro-pyrimido[1,2-a] pyrimidinateborane-bis-η⁵-inden-1-ylzirconium η⁴-1,4-dinaphthyl-1,3-butadiene;

[1106] 1,3,4,6,7,8-hexahydro-pyrimido[1,2-a] pyrimidinateborane-bis-η⁵-inden-1-ylzirconium η⁴-1-phenyl-1,3-pentadiene;

[1107] 1,3,4,6,7,8-hexahydro-pyrimido[1,2-a] pyrimidinateborane-bis-η⁵-inden-1-ylzirconium η⁴-1,3-pentadiene;

[1108] N,N′-diisopropyl-phenyl-amidinateborane-bis-η⁵-(2-methylinden-1-yl)zirconium dichloride;

[1109] N,N′-diisopropyl-phenyl-amidinateborane-bis-η⁵-(2-methylinden-1-yl)zirconium dimethyl;

[1110] N,N′-diisopropyl-phenyl-amidinateborane-bis-η⁵-(2-methylinden-1-yl)zirconium bis-dimethylamide;

[1111] N,N′-diisopropyl-phenyl-amidinateborane-bis-η⁵-(2-methylinden-1-yl)zirconium 2-methyl-1,3-butadiene;:

[1112] N,N′-diisopropyl-phenyl-amidinateborane-bis-η⁵-(2-methylinden-1-yl)zirconium 2,3-di ethyl-1,3-butadiene;

[1113] N,N′-diisopropyl-phenyl-amidinateborane-bis-η⁵-(2-methylinden-1-yl)zirconium 2-N,N-dimethylaminobenzyl;

[1114] N,N′-diisopropyl-phenyl-amidinateborane-bis-η⁵-(2-methylinden-1-yl)zirconium allyl;

[1115] N,N′-diisopropyl-phenyl-amidinateborane-bis-η⁵-(2-methylinden-1-yl)zirconiumη⁴-1,4-diphenyl-1,3-butadiene;

[1116] N,N′-diisopropyl-phenyl-amidinateborane-bis-η⁵-(2-methylinden-1-yl)zirconium η⁴-2,4-hexadiene;

[1117] N,N′-diisopropyl-phenyl-amidinateborane-bis-η⁵-(2-methylinden-1-yl)zirconiumη¹-1,4-dinaphthyl-1,3-butadiene;

[1118] N,N′-diisopropyl-phenyl-amidinateborane-bis-η⁵-(2-methylinden-1-yl)zirconium η⁴-1-phenyl-1,3-pentadiene;

[1119] N,N′-diisopropyl-phenyl-amidinateborane-bis-η⁵-(2-methylinden-1-yl)zirconium η⁴-1,3-pentadiene;

[1120] N,N′-bis-2,6-diisopropylphenyl-phenyl-amidinateborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconium dichloride;

[1121] N,N′-bis-2,6-diisopropylphenyl-phenyl-amidinateborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconium dimethyl;

[1122] N,N′-bis-2,6-diisopropylphenyl-phenyl-amidinateborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconium bis-dimethylamide;

[1123] N,N′-bis-2,6-diisopropylphenyl-phenyl-amidinateborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconium2-methyl-1,3-butadiene;

[1124] N,N′-bis-2,6-diisopropylphenyl-phenyl-amidinateborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconium2,3-dimethyl-1,3-butadiene;

[1125] N,N′-bis-2,6-diisopropylphenyl-phenyl-amidinateborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconium2-N,N-dimethylaminobenzyl;

[1126] N,N′-bis-2,6-diisopropylphenyl-phenyl-amidinateborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconium allyl;

[1127] N,N′-bis-2,6-diisopropylphenyl-phenyl-amidinateborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconiumη⁴-1,4-diphenyl-1,3-butadiene;

[1128] N,N′-bis-2,6-diisopropylphenyl-phenyl-amidinateborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconium η⁴-2,4-hexadiene;

[1129] N,N′-bis-2,6-diisopropylphenyl-phenyl-amidinateborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconiumη⁴-1,4-dinaphthyl-1,3-butadiene;

[1130] N,N′-bis-2,6-diisopropylphenyl-phenyl-amidinateborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconiumη⁴-1-phenyl-1,3-pentadiene;

[1131] N,N′-bis-2,6-diisopropylphenyl-phenyl-amidinateborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconium η⁴-1,3-pentadiene;

[1132] N,N′-bis-2,6-diisopropylphenyl-3-methyl-1,3-diketimineborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconium dichloride;

[1133] N,N′-bis-2,6-diisopropylphenyl-3-methyl-1,3-diketimineborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconium dimethyl;

[1134] N,N′-bis-2,6-diisopropylphenyl-3-methyl-1,3-diketimineborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconium bis-dimethylamide;

[1135] N,N′-bis-2,6-diisopropylphenyl-3-methyl-1,3-diketimineborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconium2-methyl-1,3-butadiene;

[1136] N,N′-bis-2,6-diisopropylphenyl-3-methyl-1,3-diketimineborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconium2,3-dimethyl-1,3-butadiene;

[1137] N,N′-bis-2,6-diisopropylphenyl-3-methyl-1,3-diketimineborane-bisη⁵-(2-methyl-4-phenylinden-1-yl)zirconium2-N,N-dimethylaminobenzyl;

[1138] N,N′-bis-2,6-diisopropylphenyl-3-methyl-1,3-diketimineborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconium allyl;

[1139] N,N′-bis-2,6-diisopropylphenyl-3-methyl-1,3-diketimineborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconiumη⁴-1,4-diphenyl-1,3-butadiene;

[1140] N,N′-bis-2,6-diisopropylphenyl-3-methyl-1,3-diketimineborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconium η⁴-2,4-hexadiene;

[1141] N,N′-bis-2,6-diisopropylphenyl-3-methyl-1,3-diketimineborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconiumη⁴-1,4-dinaphthyl-1,3-butadiene;

[1142] N,N′-bis-2,6-diisopropylphenyl-3-methyl-1,3-diketimineborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconiumη⁴-1-phenyl-1,3-pentadiene;

[1143] N,N′-bis-2,6-diisopropylphenyl-3-methyl-1,3-diketimineborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconium η⁴-1,3-pentadiene;

[1144]bis(N,N′diisopropyl-phenyl-amidinate)diborane-1,2-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconiumdichloride;

[1145]bis(N,N′-diisopropyl-phenyl-amidinate)diborane-1,2-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconiumdimethyl;

[1146]bis(N,N′-diisopropyl-phenyl-amidinate)diborane-1,2-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconiumbis-dimethylamide;

[1147]bis(N,N′-diisopropyl-phenyl-amidinate)diborane-1,2-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconium2-methyl-1,3-butadiene;

[1148]bis(N,N′-diisopropyl-phenyl-amidinate)diborane-1,2-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconium2,3-dimethyl-1,3-butadiene;

[1149]bis(N,N′-diisopropyl-phenyl-amidinate)diborane-1,2-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconium2-N,N-dimethylaminobenzyl;

[1150]bis(N,N′-diisopropyl-phenyl-amidinate)diborane-1,2-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconiumallyl;

[1151]bis(N,N′-diisopropyl-phenyl-amidinate)diborane-1,2-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconiumη⁴-1,4-diphenyl-1,3-butadiene;

[1152]bis(N,N′-diisopropyl-phenyl-amidinate)diborane-1,2-bis-1,5-(2-methyl-4-phenylinden-1-yl)zirconiumη⁴-2,4-hexadiene;

[1153]bis(N,N′-diisopropyl-phenyl-amidinate)diborane-1,2-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconiumη⁴-1,4-dinaphthyl-1,3-butadiene;

[1154]bis(N,N′-diisopropyl-phenyl-amidinate)diborane-1,2-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconiumη⁴-1-phenyl-1,3-pentadiene;

[1155]bis(N,N′-diisopropyl-phenyl-amidinate)diborane-1,2-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconiumη¹-1,3-pentadiene;

[1156]bis(N,N′-diisopropyl-3-phenyl-1,3-diketimine)diborane-1,2-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconiumdichloride;

[1157]bis(N,N′-diisopropyl-3-phenyl-1,3-diketimine)diborane-1,2-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconiumdimethyl;

[1158]bis(N,N′-diisopropyl-3-phenyl-1,3-diketimine)diborane-1,2-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconiumbis-dimethylamide;

[1159]bis(N,N′-diisopropyl-3-phenyl-1,3-diketimine)diborane-1,2-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconium2-methyl-1,3-butadiene;

[1160]bis(N,N′-diisopropyl-3-phenyl-1,3-diketimine)diborane-1,2-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconium2,3-dimethyl-1,3-butadiene;

[1161]bis(N,N′-diisopropyl-3-phenyl-1,3-diketimine)diborane-1,2-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconium2-N,N-dimethylaminobenzyl;

[1162]bis(N,N′-diisopropyl-3-phenyl-1,3-diketimine)diborane-1,2-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconiumallyl;

[1163]bis(N,N′-diisopropyl-3-phenyl-1,3-diketimine)diborane-1,2-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconiumη⁴-1,4-diphenyl-1,3-butadiene;

[1164]bis(N,N′-diisopropyl-3-phenyl-1,3-diketimine)diborane-1,2-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconiumη⁴-1,4-2,4-hexadiene;

[1165]bis(N,N′-diisopropyl-3-phenyl-1,3-diketimine)diborane-1,2-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconiumη⁴-1,4-dinaphthyl-1,3-butadiene;

[1166]bis(N,N′-diisopropyl-3-phenyl-1,3-diketimine)diborane-1,2-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconiumη⁴-1-phenyl-1,3-pentadiene;

[1167]bis(N,N′-diisopropyl-3-phenyl-1,3-diketimine)diborane-1,2-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconiumη⁴-1,3-pentadiene;

[1168] N,N′-diisopropyl-phenyl-amidinateborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)zirconium dichloride;

[1169] N,N′-diisopropyl-phenyl-amidinateborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)zirconium dimethyl;

[1170] N,N′-diisopropyl-phenyl-amidinateborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)zirconiumbis-dimethylamide;

[1171] N,N′-diisopropyl-phenyl-amidinateborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)zirconium2-methyl-1,3-butadiene;

[1172] N,N′-diisopropyl-phenyl-amidinateborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)zirconium2,3-dimethyl-1,3-butadiene;

[1173] N,N′-diisopropyl-phenyl-amidinateborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)zirconium2-N,N-dimethylaminobenzyl;

[1174] N,N′-diisopropyl-phenyl-amidinateborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)zirconium allyl;

[1175] N,N′-diisopropyl-phenyl-amidinateborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)zirconiumη⁴-1,4-phenyl-1,3-butadiene;

[1176] N,N′-diisopropyl-phenyl-amidinateborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)zirconium η⁴-2,4-hexadiene;

[1177] N,N′-diisopropyl-phenyl-amidinateborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)zirconiumη⁴-1,4-dinaphthyl-1,3-butadiene;

[1178] N,N′-diisopropyl-phenyl-amidinateborane-bis-η⁵-(2-methyl-4-naphthylinden-1yl)zirconiumη⁴-1-phenyl-1,3-pentadiene;

[1179] N,N′-diisopropyl-phenyl-amidinateborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)zirconiumη⁴-1,3-pentadiene;

[1180] N,N′-diisopropyl-3-phenyl-1,3-diketimineborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)zirconium dichloride;

[1181] N,N′-diisopropyl-3-phenyl-1,3-diketimineborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)zirconium dimethyl;

[1182] N,N′-diisopropyl-3-phenyl-1,3-diketimineborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)zirconiumbis-dimethylamide;

[1183] N,N′-diisopropyl-3-phenyl-1,3-diketimineborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)zirconium2-methyl-1,3-butadiene;

[1184] N,N′-diisopropyl-3-phenyl-1,3-diketimineborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)zirconium2,3-dimethyl-1,3-butadiene;

[1185] N,N′-diisopropyl-3-phenyl-1,3-diketimineborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)zirconium2-N,N-dimethylaminobenzyl;

[1186] N,N′-diisopropyl-3-phenyl-1,3-diketimineborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)zirconium allyl;

[1187] N,N′-diisopropyl-3-phenyl-1,3-diketimine borane-bisη⁵-(2-methyl-4-naphthylinden-1-yl)zirconiumη⁴-1,4-diphenyl-1,3-butadiene,

[1188] N,N′-diisopropyl-3-phenyl-1,3-diketimineborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)zirconium η⁴-2,4-hexadiene;

[1189] N,N′-diisopropyl-3-phenyl-1,3-diketimineborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)zirconiumη⁴-1,4-dinaphthyl-1,3-butadiene,

[1190] N,N′-diisopropyl-3-phenyl-1,3-diketimineborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)zirconium-1-phenyl-1,3-pentadiene;

[1191] N,N′-diisopropyl-3-phenyl-1,3-diketimineborane-bis-η⁵-(2-methyl-4-naphthylinden-1-yl)zirconiumη⁴-1,3-pentadiene;

[1192]bis-2,6-diisopropylphenylamido-bis(N,N′-diisopropyl-phenyl-amidinate)diboranetitanium dichloride;

[1193]bis-2,6-diisopropylphenylamido-bis(N,N′-diisopropyl-phenyl-amidinate)diboranetitanium dimethyl;

[1194]bis-2,6-diisopropylphenylamido-bis(N,N′-diisopropyl-phenyl-amidinate)diboranetitanium bis-dimethylamide;

[1195]bis-2,6-diisopropylphenylamido-bis(N,N′-diisopropyl-phenyl-amidinate)diboranetitanium 2-methyl-1,3-butadiene;

[1196]bis-2,6-diisopropylphenylamido-bis(N,N′-diisopropyl-phenyl-amidinate)diboranetitanium 2,3-dimethyl-1,3-butadiene;

[1197]bis-2,6-diisopropylphenylamido-bis(N,N′-diisopropyl-phenyl-amidinate)diboranetitanium 2-N,N-dimethylaminobenzyl;

[1198]bis-2,6-diisopropylphenylamido-bis(N,N′-diisopropyl-phenyl-amidinate)diboranetitanium allyl;

[1199]bis-2,6-diisopropylphenylamido-bis(N,N′-diisopropyl-phenyl-amidinate)diboranetitanium η⁴-1,4-diphenyl-1,3-butadiene;

[1200]bis-2,6-diisopropylphenylamido-bis(N,N′-diisopropyl-phenyl-amidinate)diboranetitanium η⁴-2,4-hexadiene;

[1201]bis-2,6-diisopropylphenylamido-bis(N,N′-diisopropyl-phenyl-amidinate)diboranetitanium η⁴-1,4-dinaphthyl-1,3-butadiene;

[1202]bis-2,6-diisopropylphenylamido-bis(N,N′-diisopropyl-phenyl-amidinate)diboranetitanium η⁴-1-phenyl-1,3-pentadiene;

[1203]bis-2,6-diisopropylphenylamido-bis(N,N′-diisopropyl-phenyl-amidinate)diboranetitanium η⁴-1,3-pentadiene;

[1204]bis-2,6-diisopropylphenylamido-bis(N,N′-diisopropyl-3-phenyl-1,3-diketimine)diboranetitanium dichloride;

[1205]bis-2,6-diisopropylphenylamido-bis(N,N′-diisopropyl-3-phenyl-1,3-diketimine)diboranetitanium dimethyl;

[1206]bis-2,6-diisopropylphenylamido-bis(N,N′-diisopropyl-3-phenyl-1,3-diketimine)diboranetitanium bis-dimethylamide;

[1207]bis-2,6-diisopropylphenylamido-bis(N,N′-diisopropyl-3-phenyl-1,3-diketimine)diboranetitanium 2-methyl-1,3-butadiene;

[1208]bis-2,6-diisopropylphenylamido-bis(N,N′-diisopropyl-3-phenyl-1,3-diketimine)diboranetitanium 2,3-dimethyl-1,3-butadiene;

[1209]bis-2,6-diisopropylphenylamido-bis(N,N′-diisopropyl-3-phenyl-1,3-diketimine)diboranetitanium 2-N,N-dimethylaminobenzyl;

[1210]bis-2,6-diisopropylphenylamido-bis(N,N′-diisopropyl-3-phenyl-1,3-diketimine)diboranetitanium allyl;

[1211]bis-2,6-diisopropylphenylamido-bis(N,N′-diisopropyl-3-phenyl-1,3-diketimine)diboranetitanium η⁴-1,4-diphenyl-1,3-butadiene;

[1212]bis-2,6-diisopropylphenylamido-bis(N,N′-diisopropyl-3-phenyl-1,3-diketimine)diboranetitanium η⁴-2,4-hexadiene;

[1213]bis-2,6-diisopropylphenylamido-bis(N,N′-diisopropyl-3-phenyl-1,3-diketimine)diboranetitanium η⁴-1,4-dinaphthyl-1,3-butadiene;

[1214]bis-2,6-diisopropylphenylamido-bis(N,N′-diisopropyl-3-phenyl-1,3-diketimine)diboranetitanium η⁴-1-phenyl-1,3-pentadiene; and

[1215]bis-2,6-diisopropylphenylamido-bis(N,N′-diisopropyl-3-phenyl-1,3-diketimine)diboranetitanium η⁴-1,3-pentadiene.

[1216] The skilled artisan will recognize that additional members of theforegoing list, such as those wherein boron is replaced by aluminum arealso included within the invention. Moreover, it should also berecognized that the terms η⁵ or η⁴ may not accurately reflect the actualelectronic distribution of the molecule under use conditions, and thatmolecules including lesser numbers of contributing atoms to theelectronic delocation are intended to be included within suchdescriptions as well.

[1217] The most highly preferred metal complexes for use herein are:

[1218] dimethylamidoborane-bis(η⁵-cyclopentadienyl)zirconium dichloride,dimethylamidoboranebis(η⁵-inden-1-yl)zirconium dichloride,dimethylamidoborane-bis(η⁵-2-methyl-4-phenylinden-1-yl)zirconiumdichloride,dimethylamidoboranebis(η⁵-2-ethyl-4-phenylinden-1-yl)zirconiumdichloride,dimethylamidoborane-bis-η⁵-2-isopropyl-4-phenylinden-1-yl)zirconiumdichloride,dimethylamidoborane-bis(η⁵-2-methyl-4-bis(η⁵-trifluoromethyl)phenylinden-1-yl)zirconiumdichloride, dimethylamidoborane-bis(η⁵-3-t-butylinden-1-yl)zirconiumdichloride,

[1219] diisopropylamidoboranebis(η⁵-cyclopentadienyl)zirconiumdichloride, diisopropylamidoboranebis(η⁵-inden-1-yl)zirconiumdichloride,diisopropylamidoborane-bis(η⁵-2-methyl-4-phenylinden-1-yl)zirconiumdichloride,diisopropylamidoborane-bis(η⁵-2-ethyl-4-phenylinden-1-yl)zirconiumdichloride,diisopropylamidoborane-bis(η⁵-2-isopropyl-4-phenylinden-1-yl)zirconiumdichloride,diisopropylamidoborane-bis(η⁵-2-methyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconiumdichloride, diisopropylamidoborane-bis(η⁵-3-t-butylinden-1-yl)zirconiumdichloride,

[1220] diphenylamidoborane-bis(η⁵-cyclopentadienyl)zirconium dichloride,diphenylamidoboranebis(η⁵-inden-1-yl)zirconium dichloride,diphenylamidoborane-bis(η⁵-2-methyl-4-phenylinden-1-yl)zirconiumdichloride,diphenylamidoborane-bis(η⁵-2-ethyl-4-phenylinden-1-yl)zirconiumdichloride,diphenylamidoborane-bis(η⁵-2-isopropyl-4-phenylinden-1-yl)zirconiumdichloride,diphenylamidoborane-bis(η⁵-2-methyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconiumdichloride, diphenylamidoborane-bis(η⁵-3-t-butylinden-1-yl)zirconiumdichloride,

[1221] dimethylamidoborane-bis(η⁵-cyclopentadienyl)zirconium1,4-diphenyl-1,3-butadiene,dimethylamidoborane-bis(η⁵-inden-1-yl)zirconium1,4-diphenyl-1,3-butadiene,dimethylamidoborane-bis(η⁵-2-methyl-4-phenylinden-1-yl)zirconium1,4-diphenyl-1,3-butadiene,dimethylamidoborane-bis(η⁵-2-ethyl-4-phenylinden-1-yl)zirconium1,4-diphenyl-1,3-butadiene,dimethylamidoborane-bis(η⁵-2-isopropyl-4-phenylinden-1-yl)zirconium1,4-diphenyl-1,3-butadiene,dimethylamidoborane-bis(η⁵-2-methyl-4-bis(3,5-trifluoromethyl)phenylinden-1-yl)zirconium1,4-diphenyl-1,3-butadiene,dimethylamidoborane-bis(η⁵-3-t-butylinden-1-yl)zirconium1,4-diphenyl-1,3-butadiene,

[1222] diisopropylamidoborane-bis(η⁵-cyclopentadienyl)zirconium1,4-diphenyl-1,3-butadiene,diisopropylamidoboranebis(η⁵-inden-1-yl)zirconium1,4-diphenyl-1,3-butadiene,diisopropylamidoborane-bis(η⁵-2-methyl-4-phenylinden-1-yl)zirconium1,4-diphenyl-1,3-butadiene,diisopropylamidoborane-bis(η⁵-2-ethyl-4-phenylinden-1-yl)zirconium1,4-diphenyl-1,3-butadiene,diisopropylamidoborane-bis(η⁵-2-isopropyl-4-phenylinden-1-yl)zirconium1,4-diphenyl-1,3-butadiene,diisopropylamidoborane-bis(η⁵-2-methyl-4-bis(η⁵-trifluoromethyl)phenylinden-1-yl)zirconium1,4-diphenyl-1,3-butadiene,diisopropylamidoborane-bis(η⁵-3-t-butylinden-1-yl)zirconium1,4-diphenyl-1,3-butadiene,

[1223] diphenylamidoborane-bis(η⁵-cyclopentadienyl)zirconium1,4-diphenyl-1,3-butadiene,diphenylamidoboranebis(η⁵-inden-1-yl)zirconium1,4-diphenyl-1,3-butadiene,diphenylamidoborane-bis(η⁵-2-methyl-4-phenylinden-1-yl)zirconium1,4-diphenyl-1,3-butadiene,diphenylamidoborane-bis(η⁵-2-ethyl-4-phenylinden-1-yl)zirconium1,4-diphenyl-1,3-butadiene,diphenylamidoborane-bis(3,5-2-isopropyl-4-phenylinden-1-yl)zirconium1,4-diphenyl-1,3-butadiene,diphenylamidoborane-bis(η⁵-2-methyl-4-bis(η⁵-trifluoromethyl)phenylinden-1-yl)zirconium1,4-diphenyl-1,3-butadiene, ordiphenylamidoborane-bis(η⁵-3-t-butylinden-1-yl)zirconium1,4-diphenyl-1,3-butadiene.

[1224] In general the complexes of the current invention can be preparedby first converting the ligands represented in formulas 1a and 2a to adianionic salt (where R⁴ is H) via reaction with an alkyl lithium,Grignard reagent, or alkali metal hydride such as NaH or KH. Thedianionic ligand derivative is then reacted with a metal complexprecursor such as MY³ ₄, MY³ ₃, or MY³ ₂ (and the corresponding-Lewisbase adducts), where Y³ is defined as above. Alternatively, reactionsemploying the neutral ligand, where R⁴ is hydrogen, in combination withthe metal precursors M(NR³ ₂)₄ or MR³ ₄ can be employed. These reactionsare conducted in an inert solvent such as a hydrocarbon solvent or aetheral solvent in the temperature range of −100° C. to 150° C.

[1225] An especially useful metal complex precursor reagent correspondsto the formula 3:

[1226] wherein M is zirconium, R¹ and LB are as previously defined andY³ each occurrence is chloride. Employment of this precursor in thereaction with ligands of this invention renders the resulting metalcomplex in high racemic purity, which is especially useful in thestereospecific polymerization of a-olefins.

[1227] Alternatively, where R⁴ in structures of formula 1 a and 2a is atrimethylsilyl group the ligand can be reacted directly with any of theabove metal complex precursors of formula 3, employing similar reactionconditions.

[1228] The recovery of the desired Group 4 transition metal complex isaccomplished by separation of the product from any alkali metal oralkaline earth metal salts and devolatilization of the reaction medium.Extraction into a secondary solvent may be. employed if desired.Alternatively, if the desired product is an insoluble precipitate,filtration or other separation techniques may be employed. Finalpurification, if required, may be accomplished by recrystallization froman inert solvent, employing low temperatures if needed.

[1229] The complexes are rendered catalytically active by combinationwith activating cocatalysts or use of activating techniques that arepreviously known in the art for use with Group 4 metal olefinpolymerization complexes. Suitable activating cocatalysts for use hereininclude polymeric or oligomeric alumoxanes, especially methylalumoxane,triisobutyl aluminum modified methylalumoxane, or isobutylalumoxane;neutral Lewis acids, such as C₁₋₃₀ hydrocarbyl substituted Group 13compounds, especially tri(hydrocarbyl)aluminum- or tri(hydrocarbyl)boroncompounds and halogenated (including perhalogenated) derivativesthereof, having from 1 to 10 carbons in each hydrocarbyl or halogenatedhydrocarbyl group, more especially perfluorinated tri(aryl)boroncompounds, and most especially tris(pentafluoro-phenyl)borane;nonpolymeric, compatible, noncoordinating, ion forming compounds(including the use of such compounds under oxidizing conditions),especially the use of ammonium-, phosphonium-, oxonium-, carbonium-,silylium- or sulfonium- salts of compatible, noncoordinating anions, orferrocenium salts of compatible, noncoordinating anions; bulkelectrolysis (explained in more detail hereinafter); and combinations ofthe foregoing activating cocatalysts and techniques. The foregoingactivating cocatalysts and activating techniques have been previouslytaught with respect to different metal complexes in the followingreferences: EP-A-277,003, U.S. Pat. No. 5,153,157, U.S. Pat. No.5,064,802, U.S. Pat. No. 5,321,106, U.S. Pat. No. 5,721,185, U.S. Pat.No. 5,350,723, U.S. Pat. No. 5,425,872, U.S. Pat. No. 5,625,087, U.S.Pat. No. 5,883,204, U.S. Pat. No. 5,919,983, U.S. Pat. No. 5,783,512, WO99/15534, and U.S. Ser. No. 09/251,664, filed Feb. 17, 1999.

[1230] Combinations of neutral Lewis acids, especially the combinationof a trialkylaluminum compound having from 1 to 4 carbons in each alkylgroup and a halogenated tri(hydrocarbyl)boron compound having from 1 to20 carbons in each hydrocarbyl group, especiallytris(pentafluorophenyl)borane, further combinations of such neutralLewis acid mixtures with a polymeric or oligomeric alumoxane, andcombinations of a single neutral Lewis acid, especiallytris(pentafluorophenyl)borane with a polymeric or oligomeric alumoxaneare especially desirable activating cocatalysts. Preferred molar ratiosof Group 4 metal complex:tris(pentafluoro-phenylborane:alumoxane arefrom 1:1:1 to 1:10:30, more preferably from 1:1:1.5 to 1:5:10.

[1231] Suitable ion forming compounds useful as cocatalysts in oneembodiment of the present invention comprise a cation which is aBronsted acid, capable of donating a proton, and a compatible,noncoordinating anion, A. As used herein, the term “noncoordinating”means an anion or substance which either does not coordinate to theGroup 4 metal containing precursor complex and the catalytic derivativederived therefrom, or which is only weakly coordinated to such complexesthereby remaining sufficiently labile to be displaced by a neutral Lewisbase. A noncoordinating anion. specifically refers to an anion whichwhen functioning as a charge balancing anion in a cationic metal complexdoes not transfer an anionic substituent or fragment thereof to saidcation thereby forming neutral complexes. “Compatible anions” are anionswhich are not degraded to neutrality when the initially formed complexdecomposes and are noninterfering with desired subsequent polymerizationor other uses of the complex.

[1232] Preferred anions are those containing a single coordinationcomplex comprising a charge-beadng metal or metalloid core which anionis capable of balancing the charge of the active catalyst species (themetal cation) which may be formed when the two components are combined.Also, said anion should be sufficiently labile to be displaced byolefinic, diolefinic and acetylenically unsaturated compounds or otherneutral Lewis bases such as ethers or nitrites. Suitable metals include,but are not limited to, aluminum, gold and platinum. Suitable metalloidsinclude, but are not limited to, boron, phosphorus, and silicon.Compounds containing anions which comprise coordination complexescontaining a single metal or metalloid atom are, of course, well knownand many, particularly such compounds containing a single boron atom inthe anion portion, are available commercially.

[1233] Preferably such cocatalysts may be represented by the followinggeneral formula:

(L*−H)_(d) ⁺(A)^(d−)

[1234] wherein:

[1235] L* is a neutral Lewis base;

[1236] (L*−H)⁺ is a conjugate Bronsted acid of L*;

[1237] A^(d−) is a noncoordinating, compatible anion having a charge ofd−, and

[1238] d is an integer from 1 to 3.

[1239] More preferably A^(d−) corresponds to the formula: [M′Q₄]⁻;

[1240] wherein:

[1241] M′ is boron or aluminum in the +3 formal oxidation state; and

[1242] Q independently each occurrence is selected from hydride,dialkylamido, halide, hydrocarbyl, hydrocarbyloxide, halo-substitutedhydrocarbyl, halo-substituted hydrocarbyloxy, and halo- substitutedsilylhydrocarbyl radicals (including perhalogenated hydrocarbyl-perhalogenated hydrocarbyloxy- and- perhalogenated silylhydrocarbylradicals), said Q having, up to 20 carbons with the proviso that in notmore than one occurrence is Q halide. Examples of suitablehydrocarbyloxide Q groups are disclosed in U.S. Pat. No. 5,296,433, theteachings of which are herein incorporated by reference.

[1243] In a more preferred embodiment, d is one, that is, the counterion has a single negative charge and is A⁻. Activating cocatalystscomprising boron which are particularly useful in the preparation ofcatalysts of this invention may be represented by the following generalformula:

(L*−H)⁺(BQ₄)⁻;

[1244] wherein:

[1245] L* is as previously defined;

[1246] B is boron in a formal oxidation state of 3; and

[1247] Q is a hydrocarbyl-, hydrocarbyloxy-, fluorinated hydrocarbyl-,fluorinated hydrocarbyloxy-, or fluorinated silylhydrocarbyl- group ofup to 20 nonhydrogen atoms, with the proviso that in not more than oneoccasion is Q hydrocarbyl.

[1248] Preferred Lewis base salts are ammonium salts, more preferablytrialkylammonium salts containing one or more C₁₂₋₄₀ alkyl groups. Mostpreferably, Q is each occurrence a fluorinated aryl group, especially, apentafluorophenyl group.

[1249] Illustrative, but not limiting, examples of boron compounds whichmay be used as an activating cocatalyst in the preparation of theimproved catalysts of this invention are

[1250] tri-substituted ammonium salts such as:

[1251] trimethylammonium tetrakis(pentafluorophenyl) borate,

[1252] trimethylammonium tetrakis(pentafluorophenyl) borate,

[1253] tripropylammonium tetrakis(pentafluorophenyl) borate,

[1254] tri(n-butyl)ammonium tetrakis(pentafluorophenyl) borate,

[1255] tri(sec-butyl)ammonium tetrakis(pentafluorophenyl) borate,

[1256] N,N-dimethylanilinium tetrakis(pentafluorophenyl) borate,

[1257] N,N-dimethylanilinium n-butyltris(pentafluorophenyl) borate,

[1258] N,N-dimethylanilinium benzyltris(pentafluorophenyl) borate,

[1259] N,N-dimethylaniliniumtetrakis(4-(t-butyldimethylsilyl)-2,3,5,6-tetrafluorophenyl) borate,

[1260] N,N-dimethylaniliniumtetrakis(4-(triisopropylsilyl)-2,3,5,6-tetrafluorophenyl) borate,

[1261] N,N-dimethylanilinium pentafluorophenoxytris(pentafluorophenyl)borate,

[1262] N,N-diethylanilinium tetrakis(pentafluorophenyl) borate,

[1263] N,N-dimethyl-2,4,6-trimethylanilinium tetrakis(pentafluorophenyl)borate,

[1264] dimethyltetradecylammonium tetrakis(pentafluorophenyl) borate,

[1265] dimethylhexadecylammonium tetrakis(pentafluorophenyl) borate,

[1266] dimethyloctadecylammonium tetrakis(pentafluorophenyl) borate,

[1267] methylditetradecylammonium tetrakis(pentafluorophenyl) borate,

[1268] methylditetradecylammonium (hydroxyphenyl)tris(pentafluorophenyl)borate,

[1269] methylditetradecylammonium(diethylaluminoxyphenyl)tris(pentafluorophenyl) borate,

[1270] methyldihexadecylammonium tetrakis(pentafluorophenyl) borate,

[1271] methyldihexadecylammonium (hydroxyphenyl)tris(pentafluorophenyl)borate,

[1272] methyldihexadecylammonium(diethylaluminoxyphenyl)tris(pentafluorophenyl) borate,

[1273] methyldioctadecylammonium tetrakis(pentafluorophenyl) borate,

[1274] methyldioctadecylammonium (hydroxyphenyl)tris(pentafluorophenyl)borate,

[1275] methyldioctadecylammonium(diethylaluminoxyphenyl)tris(pentafluorophenyl) borate, mixtures of theforegoing,

[1276] dialkyl ammonium salts such as:

[1277] di-(i-propyl)ammonium tetrakis(pentafluorophenyl) borate,

[1278] methyloctadecylammonium tetrakis(pentafluorophenyl) borate,

[1279] methyloctadodecylammonium tetrakis(pentafluorophenyl) borate, and

[1280] dioctadecylammonium tetrakis(pentafluorophenyl) borate;

[1281] tri-substituted phosphonium salts such as:

[1282] triphenylphosphonium tetrakis(pentafluorophenyl) borate,

[1283] methyldioctadecylphosphonium tetrakis(pentafluorophenyl) borate,and

[1284] tri(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorophenyl)borate;

[1285] di-substituted oxonium salts such as:

[1286] diphenyloxonium tetrakis(pentafluorophenyl) borate,

[1287] di(o-tolyl)oxonium tetrakis(pentafluorophenyl) borate, and

[1288] di(octadecyl)oxonium tetrakis(pentafluorophenyl) borate;

[1289] di-substituted sulfonium salts such as:

[1290] di(o-tolyl)sulfonium tetrakis(pentafluorophenyl) borate, and

[1291] methylcotadecylsulfonium tetrakis(pentafluorophenyl) borate.

[1292] Preferred (L*−H)⁺ cations are methyldioctadecylammonium anddimethyloctadecylammonium.

[1293] Another suitable ion forming, activating cocatalyst comprises asalt of a cationic oxidizing agent and a noncoordinating, compatibleanion represented by the formula:

(Ox^(e+))_(d)(A^(d−))_(e).

[1294] wherein:

[1295] Ox^(e+) is a cationic oxidizing agent having a charge of e+;

[1296] e is an integer from 1 to 3; and

[1297] A^(d−) and d are as previously defined.

[1298] Examples of cationic oxidizing agents include: ferrocenium,hydrocarbyl-substituted ferrocenium, Ag⁺ or Pb⁺². Preferred embodimentsof A^(d−) are those anions previously defined with respect to theBronsted acid containing activating cocatalysts, especiallytetrakis(pentafluorophenyl)borate.

[1299] Another suitable ion forming, activating cocatalyst comprises acompound which is a salt of a carbenium ion and a noncoordinating,compatible anion represented by the formula:

{circle over (c)}⁺A⁻

[1300] wherein:

[1301] {circle over (c)}⁺ is a C₁₋₂₀ carbenium ion; and

[1302] A⁻is as previously defined. A preferred carbenium ion is thetrityl cation, i.e. triphenylmethylium.

[1303] A further suitable ion forming, activating cocatalyst comprises acompound which is a salt of a silylium ion and a noncoordinating,compatible anion represented by the formula:

R₃Si(X′)_(q) ⁺A⁻

[1304] wherein:

[1305] R is C₁₋₁₀ hydrocarbyl, and X′, q and A⁻ are as previouslydefined.

[1306] Preferred silylium salt activating cocatalysts aretrimethylsilylium tetrakispentafluorophenylborate, trimethylsilyliumtetrakispentafluorophenylborate and ether substituted adducts thereof.Silylium salts have been previously generically disclosed in J. Chem.Soc. Chem. Comm., 1993, 383-384, as well as Lambert, J. B., et al.,Organometallics, 1994, 13, 2430-2443. The use of the above silyliumsalts as activating cocatalysts for addition polymerization catalysts isdisclosed in U.S. Ser. No. 304,314, filed Sep. 12, 1994, published inequivalent form as WO96/08519 on Mar. 21, 1996, the teachings of whichare herein incorporated by reference.

[1307] Certain complexes of alcohols, mercaptans, silanols, and oximeswith tris(pentafluorophenyl)borane are also effective catalystactivators and may be used according to the present invention. Suchcocatalysts are disclosed in U.S. Pat. No. 5,296,433, the teachings ofwhich are herein incorporated by reference.

[1308] Another class of suitable catalyst activators are expandedanionic compounds corresponding to the formula: (A^(1+a))_(b) ¹(Z¹J¹_(j) ¹)^(−c1)d¹,

[1309] wherein:

[1310] A¹ is a cation of charge +a¹,

[1311] Z¹ is an anion group of from 1 to 50, preferably 1 to 30 atoms,not counting hydrogen atoms, further containing two or more Lewis basesites;:

[1312] J¹ independently each occurrence is a Lewis acid coordinated toat least one Lewis base site of Z¹, and optionally two or more such J¹groups may be joined together in a moiety having multiple Lewis acidicfunctionality,

[1313] j¹ is a number from 2 to 12 and

[1314] a¹, b¹, c¹, and d¹ are integers from 1 to 3, with the provisothat a¹×b¹ is equal to c¹×d¹.

[1315] The foregoing cocatalysts (illustrated by those havingimidazolide, substituted imidazolide, imidazolinide, substitutedimidazolinide, benzimidazolide, or substituted benzimidazolide anions)may be depicted schematically as follows:

[1316] wherein:

[1317] A¹⁺ is a monovalent cation as previously defined, and preferablyis a trihydrocarbyl ammonium cation, containing one or two C₁₀₋₄₀ alkylgroups, especially the methylbis(tetradecyl)ammonium- ormethylbis(octadecyl)ammonium- cation,

[1318] R⁸, independently each occurrence, is hydrogen or a halo,hydrocarbyl, halocarbyl, halohydrocarbyl, silylhydrocarbyl, or silyl,(including mono-, di- and tri(hydrocarbyl)silyl) group of up to 30 atomsnot counting hydrogen, preferably C₁₋₂₀ alkyl, and

[1319] J¹ is tris(pentafluorophenyl)borane ortris(pentafluorophenyl)aluminane.

[1320] Examples of these catalyst activators include thetrihydrocarbylammonium-, especially, methylbis(tetradecyl)ammonium- ormethylbis(octadecyl)ammonium- salts of:

[1321] bis(tris(pentafluorophenyl)borane)imidazolide,

[1322] bis(tris(pentafluorophenyl)borane)-2-undecylimidazolide,

[1323] bis(tris(pentafluorophenyl)borane)-2-heptadecylimidazolide,

[1324] bis(tris(pentafluorophenyl)borane)-4,5-bis(undecyl)imidazolide,

[1325]bis(tris(pentafluorophenyl)borane)-4,5-bis(heptadecyl)imidazolide,

[1326] bis(tris(pentafluorophenyl)borane) imidazolinide,

[1327] bis(tris(pentafluorophenyl)borane)-2-undecylimidazolinide,

[1328] bis(tris(pentafluorophenyl)borane)-2-heptadecylimidazolinide,

[1329] bis(tris(pentafluorophenyl)borane)-4,5-bis(undecyl)imidazolinide,

[1330]bis(tris(pentafluorophenyl)borane)-4,5-bis(heptadecyl)imidazolinide,

[1331] bis(tris(pentafluorophenyl)borane)-5,6-dimethylbenzimidazolide,

[1332]bis(tris(pentafluorophenyl)borane)-5,6-bis(undecyl)benzimidazolide,

[1333] bis(tris(pentafluorophenyl)alumane)imidazolide,

[1334] bis(tris(pentafluorophenyl)alumane)-2-undecylimidazolide,

[1335] bis(tris(pentafluorophenyl)alumane)-2-heptadecylimidazolide,

[1336] bis(tris(pentafluorophenyl)alumane)-4,5-bis(undecyl)imidazolide,

[1337]bis(tris(pentafluorophenyl)alumane)-4,5-bis(heptadecyl)imidazolide

[1338] bis(tris(pentafluorophenyl)alumane)imidazolinide,

[1339] bis(tris(pentafluorophenyl)alumane)-2-undecylimidazolinide,

[1340] bis(tris(pentafluorophenyl)alumane)-2-heptadecylimidazolinide,

[1341]bis(tris(pentafluorophenyl)alumane)-4,5-bis(undecyl)imidazolinide,

[1342]bis(tris(pentafluorophenyl)alumane)-4,5-bis(heptadecyl)imidazolinide,

[1343] bis(tris(pentafluorophenyl)alumane)-5,6-dimethylbenzimidazolide,and

[1344]bis(tris(pentafluorophenyl)alumane)-5,6-bis(undecyl)benzimidazolide.

[1345] The molar ratio of catalyst/cocatalyst employed preferably rangesfrom 1:10,000 to 100:1, more preferably from 1:5000 to 10:1, mostpreferably from 1:1000 to 1:1. Alumoxane, when used by itself as anactivating cocatalyst, is employed in large quantity, generally at least100 times the quantity of metal complex on a molar basis.Tris(pentafluorophenyl)borane, where used as an activating cocatalyst isemployed in a molar ratio to the metal complex of form 0.5:1 to 10:1,more preferably from 1:1 to 6:1 most preferably from 1:1 to 5:1. Theremaining activating cocatalysts are generally employed in a molar ratioto the metal complex from 0.9:1 to 3:1, and preferably in approximatelyan equimolar quantity with the metal complex, that is from 1.1 to 1.5:1.

[1346] The catalyst composition may be prepared and employed as aheterogeneous catalyst by adsorbing, depositing or chemically attachingthe requisite components on an inert inorganic or organic particulatedsolid. Examples of such solids include, silica, silica gel, alumina,clays, expanded clays (aerogels), aluminosilicates, trialkylaluminumcompounds, and organic or inorganic polymeric materials, especiallypolyolefins. In an preferred embodiment, a heterogeneous catalyst isprepared by reacting an inorganic compound, preferably a tri(C₁₋₄ alkylaluminum compound, with an activating cocatalyst, especially:an ammoniumsalt of a hydroxyaryl(trispenta-fluorophenyl)borate, such as an ammoniumsalt of (4-hydroxy-3,5-ditertiarybutylphenyl)tris-(pentafluorophenylborate or (4-hydroxyphenyl)-tris(pentafluorophenyl)borate. Thisactivating cocatalyst is deposited onto the support by coprecipitating,imbibing, spraying, or similar technique, and thereafter removing anysolvent or diluent. The metal complex is added to the support, also byadsorbing, depositing or chemically attaching the same to the support,either subsequently, simultaneously or prior to addition of theactivating cocatalyst.

[1347] The catalysts, preferably supported in any of the foregoingmethods, may be used to polymerize ethylenically and/or acetylenicallyunsaturated monomers having from 2 to 8 carbon atoms either alone or incombination in the gas phase. Preferred monomers include the C₂₋₆α-olefins especially ethylene, propylene, isobutylene, 1-butene,1-pentene, 1-hexene, 3-methyl-1-pentene, 4-methyl-1-pentene, andmixtures thereof. Other preferred monomers include 1,3-butadiene,ethylidenenorbornene, and mixtures thereof. Preferred monomers includeethylene, or a mixture of C₂₋₆ α-olefins.

[1348] Long chain macromolecular a-olefins are vinyl terminatedpolymeric remnants formed in situ, especially during continuous orsemi-continuous polymerization reactions. Under suitable processingconditions such long chain macromolecular units are readily polymerizedinto the polymer product along with ethylene and other short chainolefin monomers to give small quantities of long chain branching in theresulting polymer. Such polymers possess improved Theologicalproperties, especially improved extrusion characteristics compared topolymers containing relatively less long chain branching. One analyticalmeasurement that may indicate the presence of long chain branching in anolefin polymer is the presence of an elevated I10/I2 or an elevatedI21/I2 value, while possessing narrow molecular weight distribution asdetermined by Mw/Mn, compared to polymers not having long chainbranching. Preferred are such polymers having Mw/Mn less than 3.5,especially less than 3.0, especially less than 2.8 and I10/I2 of greaterthan 10, preferably greater than 20, most preferably greater than 30.

[1349] In general, the polymerization may be accomplished at conditionswell known in the prior art for gas phase polymerization reactions, thatis, temperatures from 0-250° C., preferably 60 to 150° C., morepreferably from 70,to 110° C. and pressures from atmospheric to 10,000atmospheres. A support, especially silica, alumina, or a polymer(especially poly(tetrafluoroethylene) or a polyolefin) may be employed,and desirably is employed to obtain a desired, particulated, polymermorphology. The support is preferably employed in an amount to provide aweight, ratio of catalyst (based on metal):support from 1:100,000 to1:10, more preferably from 1:50,000 to 1:20, and most preferably from1:10,000 to 1:30. In most polymerization reactions the molar ratio ofcatalyst:polymerizable compounds employed is from 10-12:.1 to 10⁻¹:1,more preferably from10⁻⁹:1 to10⁻⁵:1.

[1350] At all times, the individual ingredients as well as the recoveredcatalyst components must be protected from oxygen and moisture.Therefore, the catalyst components and catalysts must be prepared andrecovered in an oxygen and moisture free atmosphere. Preferably,therefore, the reactions are performed in the presence of an dry, inertgas such as, for example, nitrogen.

[1351] Gas phase processes for the polymerization of olefins, especiallythe homopolymerization and copolymerization of ethylene and propylene,and the copolymerization of ethylene with higher α-olefins are wellknown in the art. The polymerization may be carried out as a batchwiseor a continuous polymerization process A continuous process ispreferred, in which event catalyst, ethylene, comonomer, and optionallysolvent are continuously supplied to the reaction zone and polymerproduct continuously removed, or intermittently removed therefrom. Thegas phase process employed can be, for example, of the type whichemploys a mechanically stirred bed or a gas fluidized bed as thepolymerization reaction zone. Preferred is the process wherein thepolymerization reaction is carried out in a vertical cylindricalpolymerization reactor containing a fluidized bed of polymer particlessupported above a perforated plate, the fluidization grid, by a flow offluidization gas.

[1352] Cooling of the reactor may be provided by the use of recycle gas,which is fed as a volatile liquid to the bed to provide an evaporativecooling effect. The volatile liquid employed in this case can be, forexample, a volatile inert liquid, for example, a saturated hydrocarbonhaving about 3 to about 8, preferably 4 to 6, carbon atoms. In the casethat the monomer or comonomer itself is a volatile liquid (or can becondensed to provide such a liquid) this can be fed to the bed toprovide an evaporative cooling effect. The volatile liquid evaporates inthe hot fluidized bed to form gas which mixes with the fluidizing gas.If the volatile liquid is a monomer or comonomer, it will undergo somepolymerization in the bed. The evaporated liquid then emerges from thereactor as part of the hot recycle gas, and enters the compression/heatexchange part of the recycle loop. The recycle gas is cooled in the heatexchanger and, if the temperature to which the gas is cooled is belowthe dew point, liquid will condense from the gas. This liquid isdesirably recycled continuously to the fluidized bed. It is possible torecycle the condensed liquid to the bed as liquid droplets carried inthe recycle gas stream. This type of, process is described, for examplein EP-A-089691; U.S. Pat. No. 4,543,399; WO 94/25495 and U.S. Pat. No.5,352,749. A particularly preferred method of recycling the liquid tothe bed is to separate the liquid from the recycle gas stream and toreinject this liquid directly into the bed, preferably using a methodwhich generates fine droplets of the liquid within the bed. This type ofprocess is described in WO 94/28032.

[1353] The polymer is produced directly in the fluidized bed bycatalyzed copolymerization of the monomer and one or more comonomers onthe fluidized particles of catalyst, supported catalyst or prepolymerwithin the bed. Start-up of the polymerization reaction is desirablyachieved using a bed of preformed polymer particles, which arepreferably similar to the target polyolefin, and conditioning the bedaccording to techniques that are well known in the art. Such processesare used commercially on a large scale for the manufacture of highdensity polyethylene (HDPE), medium density polyethylene (MDPE), linearlow density polyethylene (LLDPE) and polypropylene.

[1354] The gas employed to fluidize the bed comprises the monomer ormonomers to be polymerized, and also serves as a heat exchange medium toremove the heat of reaction from the bed. The hot gases emerge from thetop of the reactor, normally via a tranquilization zone, also known as avelocity reduction zone, having a larger cross-sectional area than thefluidized bed and wherein fine particles entrained in the gas streamhave an opportunity to gravitate back into the bed. It can also beadvantageous to use a cyclone to remove fine particles from the hot gasstream. The gas is then normally recycled to the bed by means of ablower or compressor and one or more heat exchangers to strip the gas ofthe heat of polymerization. The produced polymer is dischargedcontinuously or discontinuously from the fluidized: bed as desired.

[1355] Typically the molar ratio of comonomer to monomer used in thepolymerization depends upon the desired density for the compositionbeing produced and is desirably about 0.5 or less. Desirably, whenproducing materials with a density range of from about 0.91 to about0.93 the comonomer to monomer ratio is less than 0.2, preferably lessthan 0.05, even more preferably less than 0.02, and may even be lessthan 0.01. Hydrogen may be added to the reaction in order to control themolecular weight and melt index of the polymer. Typically, the ratio ofhydrogen to monomer is less than about 0.5, preferably less than 0.2,more preferably less than 0.05, even more preferably less than 0.01.

[1356] A number of patents and patent applications describe gas phaseprocesses which are adaptable for use in the process of this invention,particularly, U.S. Pat. Nos. 4,588,790; 4,543,399; 5,352,749; 5,436,304;5,405,922; 5,462,999; 5,461,123; 5,453,471; 5,032,562; 5,028,670;5,473,028; 5,106,804; 5,541,270, EP-A-659,773; EP-A-692,500; WO94/29032, WO 94/25497, WO 94/25495, WO 94/28032; WO 95/13305; WO94/26793; and WO 95/07942

EXAMPLES

[1357] The skilled artisan will appreciate that the invention disclosedherein may be practiced in the absence of any component which has notbeen specifically disclosed. The following examples are provided asfurther illustration of the invention and are not to be construed aslimiting. Unless stated to the contrary all parts and percentages areexpressed on a weight basis. The term “overnight”, if used, refers to atime of approximately 16-18 hours, the term “room temperature”, refersto a temperature of about 20-25° C., and the term “mixed alkanes” refersto a commercially obtained mixture of C₆₋₈ aliphatic hydrocarbonsavailable under the trade designation Isopar E®, from Exxon ChemicalsInc.

[1358]¹H (300 MHz) and ¹³C NMR (75 MHz) spectra were recorded on aVarian XL-300 spectrometer. ¹H and ¹³C NMR spectra are referenced to theresidual solvent peaks and are reported in ppm relative totetramethylsilane. All J Values are given in Hz. Tetrahydrofuran (THF),diethylether, toluene, and hexane were used following passage throughdouble columns charged with activated alumina and a purifying catalyst(Q-5® available from Englehardt Chemicals Inc.) The compounds BCl₃—SMe₂,BBr₃—SMe₂, B(NMe₂)₃, n-BuLi were all used as purchased from Aldrich. Thecompound TiCl₃(THF)₃ was prepared as described in the literature. Allsyntheses were performed under dry nitrogen or argon atmospheres using acombination of glove box and high vacuum techniques.

Example 1Dichloro-[1,2-Bis(2,6-diisopropylanilide)-1,2-bis(dimethylamido)diborane]titanium

[1359]

[1360] 1A) Preparation of Chlorobis(dimethylamido)borane, (modificationof Chavant, P. Y.; Vaultier, M. J. Organomet. Chem. 1993, 455, 37-46)

[1361] BCl₃—SMe₂ (62.000 g, 345.78 mmol) and B(NMe₂)₃ (98.921 g, 691.56mmole) were stirred together at room temperature overnight under anitrogen bubbler. The mixture was then heated to reflux for one hour todrive off any residual SMe₂. Allowing the pale yellow liquid to stir toroom temperature resulted in the isolation of the desired productcleanly (44.979 g, 99.9 percent yield).

[1362]¹H NMR (C₆D₆): δ 2.49 (s, 12 H). ¹³C NMR (C₆D₆): δ 39.86.

[1363] 1B) Preparation of Tetrakis(dimethylamido)diborane (modificationof Noth, H; Meister, W. Z. Naturforsch., Teil B 1962, 17, 714)

[1364] Chlorobis(dimethylamido)borane (30.000 g, 223.19 mmol) wasrefluxed in hexane (200 ml) as Na/K alloy [Na (1.539 g, 66.96mmol)/8.726 g K (8.726 g, 223.19 mmol)] was added dropwise to thesolution. After the first several drops the reaction initiated asevidenced by a sudden increase in the reflux. The heat was then turnedoff and the alloy added slowly so as to maintain a reflux. After theaddition was complete, the reaction mixture was heated to reflux for anadditional hour and then stirred at room temperature for three hours.The mixture was then filtered through a pad of diatomaceous earth andthe volatiles removed resulting in the isolation of a yellow liquid.Fractional vacuum distillation resulted in the isolation of the desiredcompound as a pale yellow liquid (7.756 g, 35.1 percent yield).

[1365]¹H NMR (C₆D6): δ2.74 (s, 24 H). ¹³C NMR (C₆D₆): δ41.34.

[1366] 1C) Preparation of Bis(dimethylamido)diborondichloride(modification of Noth, H; Meister, W. Z. Naturforsch., Teil B 1962, 17,714)

[1367] Tetrakis(dimethylamido)diborane (7.76 g, 39.29 mmol) was stirredin diethylether (100 ml) at −78° C. as HCl (157 mmol,157 ml of 1.0 Msolution in diethylether) was added dropwise. This mixture was thenallowed to stir for six hours at room temperature. After the reactionperiod the volatiles were removed and the residue extracted and filteredusing hexane. Removal of the hexane resulted in the isolation of ayellow oil. Fractional vacuum distillation resulted in the isolation ofthe desired compound as a pale yellow liquid (4.72 g, 66.7 percentyield).

[1368]¹H NMR (C₆D₆): δ2.40 (s, 6 H), 2.50 (s, 6 H). ¹³C NMR (C₆D₆):δ37.62, 41.78.

[1369] 1D) Preparation of 2,6-Diisopropylaniline, lithium salt

[1370] n-BuLi (56.4 mmol, 35.3 ml of 1.60 M solution in hexane) wasadded dropwise to a solution of 2,6-diisopropylaniline (10.0 g, 56.4mmol) in hexane (100 ml). This mixture was allowed to stir for 3 hoursduring which time a white precipitate formed. After the reaction periodthe mixture was filtered and the white salt washed with hexane and driedunder vacuum and used without further purification or analysis (9.99 g,96.7 percent).

[1371] 1E) Preparation of1,2-Bis(2,6-diisopropylanilide)-1,2-bis(dimethylamido)diborane

[1372] Bis(dimethylamido)diborondichloride (2.35 g, 13.0 mmol) indiethylether (10 ml) was added dropwise to a solution of2,6-diisopropylaniline, lithium salt (4.77 g, 26.0 mmol) in diethylether(50 ml) at 0° C. This mixture was then allowed to stir overnight at roomtemperature. After the reaction period the volatiles were removed andthe residue extracted and filtered using hexane. Removal of the hexaneresulted in the isolation of a the desired product as a white solid(5.32 g, 88.9 percent yield).

[1373]¹H NMR (C₆D₆, RT): δ0.9-1.4 (br m, 24 H), 2.3 (s, 6 H),2.8 (s,6H), 3.7 (s, 2 H), 7.0(brs, 6 H).

[1374] 1F) Preparation of1,2-Bis(2,6-diisopropylanilide)-1,2-bis(dimethylamido)diborane,dilithium salt

[1375] 1,2-Bis(2,6-diisopropylanilide)-1,2-bis(dimethylamido)diborane(1.82 g, 3.95 mmol) was stirred in hexane (75 ml) as n-BuLi (7.91 mmol,4.94 ml of 1.60 M solution in hexane) was-added dropwise. This mixturewas then allowed to stir overnight. After the reaction period themixture was filtered and the salt washed well with hexane and driedunder vacuum resulting in the isolation of the desired product as awhite powder (1.69 g, 90.4 percent yield);.

[1376] 1G) Preparation ofDichloro-[1,2-Bis(2,6-diisopropylanilide)-1,2-bis(dimethylamido)diborane]titanium

[1377] 1,2-Bis(2,6-diisopropylanilide)-1,2-bis(dimethylamido)diborane,dilithium salt (0.60 g, 1.27 mmol) in THF (20 ml) was added dropwise toa slurry of TiCl₃(THF)₃ (0.47 g, 1.27 mmol) in THF (50 ml) at 0° C. Thismixture was then allowed to stir at room temperature for 45 minutes.PbCl₂ (0.177 g, 0.640 mmol) was then added as a solid and the mixtureallowed to stir for an additional 30 minutes. After the reaction periodthe volatiles were removed and the residue extracted and filtered usinghexane. Concentration of the hexane and cooling to −10° C. overnightresulted in the formation of-orange X-ray quality crystals (0.156 g,21.3 percent yield).

[1378]¹H NMR (C₆D₆): δ1.23 (d, ³J_(HH)=6.6 Hz, 6 H), 1.45 (d,³J_(HH)=6.6 Hz, 6 H), 2.17 (s, 6 H), 2.76 (s, 6 H), 3.53 (septet,³J_(HH)=6.6 Hz, 4 H), 7.11 (s, 6 H)

Example 2 Dichloro[1,2-Bis(2,6-diisopropylanilide)-1,2-bis(dimethylamido)diborane]titanium(alternated preparation)

[1379] 2A) Preparation of Chlorobis(dimethylamido)borane.

[1380] BCl₃—SMe₂ (62.000 g, 345.78 mmol) and B(NMe₂)₃ (98.921 g, 691.56mmol) were stirred together at room temperature overnight under anitrogen bubbler. The mixture was then heated to reflux for one hour todrive off any residual SMe₂. Allowing the pale yellow liquid to stir toroom temperature resulted in the isolation of the desired product(139.436 g, 93.3 percent yield).

[1381]¹H NMR (C₆D₆): δ2.49 (s, 12 H). ¹³C NMR (C₆D₆): δ39.86.

[1382] 2B) Preparation of Tetrakis(dimethylamido)diborane via ClB(NMe)₂.

[1383] Chlorobis(dimethylamido)borane (30.000 g, 223.19 mmol) wasrefluxed in hexane (200 ml) as Na/K alloy [Na (1.539 g, 66.96mmol)/8.726 g K (8.726 g, 223.19 mmol)] was added dropwise to thesolution. After the first several drops the reaction initiated asevidenced by a sudden increase in the reflux. The heat was then turnedoff and the alloy added slowly so as to maintain a reflux. After theaddition was complete, the reaction mixture was heated to reflux for anadditional hour and then stirred at room temperature for three hours.The mixture was then filtered through a diatomaceous earth pad and thevolatile components were removed resulting in the isolation of a yellowliquid. Fractional vacuum distillation resulted in the isolation of thedesired compound as a pale yellow liquid (7.756 g, 35.1 percent yield).

[1384]¹H NMR (C₆D₆): δ 2.73(s, 24 H). ¹³C NMR (C₆D₆): δ 41.37.

[1385] 2C) Preparation of Tetrakis(dimethylamido)diborane viaBis(catecholato)diboron.

[1386] Lithium dimethylamide (10.70 g, 210.0 mmol) was added slowly as asolid to a solution of bis(catecholato)diboron (10.00 g, 42.00 mmol) indiethylether (200 ml) at −20° C. This mixture was then allowed to stirfor an additional 40 hours at room temperature. After the reactionperiod the ether was removed under vacuum and the residue extracted andfiltered using hexane. Removal of the hexane resulted in the isolationof a yellow oil. Fractional vacuum distillation resulted in theisolation of the desired compound as a pale yellow liquid (5.493 g, 66.0percent yield).

[1387] 2D) Preparation of Bis(dimethylamido)diborondichloride.

[1388] Tetrakis(dimethylamido)diborane (7.756 g, 39.19 mmol) was stirredin diethylether (100 ml) at −78° C. as HCl (156.75 mmol,156.75 ml of 1.0M solution in diethylether) was added dropwise. This mixture was thenallowed to stir for six hours at room temperature. After the reactionperiod the volatile components were removed and the residue extractedand filtered using hexane. Removal of the hexane resulted in theisolation of a yellow oil. Fractional vacuum distillation resulted inthe isolation of the desired compound as a pale yellow liquid (4.722 g,66.7 percent yield).

[1389]¹H NMR (C₆D₆): δ 2.40 (s, 6 H), 2.50 (s, 6 H). ¹³C NMR (C₆D₆):δ37.62, 41.78.

[1390] 2E) Preparation of 2,6-Diisopropylaniline, lithium salt.

[1391] n-BuLi (56.40 mmol, 35.25 ml of 1.6 M solution in hexane) wasadded dropwise to a solution of 2,6-diisopropylaniline (10.00 g, 56.40mmol) in hexane (100 ml). This mixture was allowed to stir for 3 hoursduring which time a white precipitate formed. After the reaction periodthe mixture was filtered and the white salt washed with hexane and driedunder vacuum and used without further purification or analysis (9.988 g,96.7 percent yield).

[1392] 2F) Preparation of1,2-Bis(2,6-diisopropylanilide)-1,2-bis(dimethylamido)diborane.

[1393] Bis(dimethylamido)diborondichloride (2.350 g, 13.00 mmol) indiethylether (10 ml) was added dropwise to a solution of2,6-diisopropylaniline, lithium salt (4.765 g, 26.01 mmol) indiethylether (50 ml) at 0° C. This mixture was then allowed to stirovernight at room temperature. After the reaction period the volatileswere removed and the residue was extracted and filtered using hexane.Removal of the hexane resulted in the isolation of a the desired productas a white solid (5.322 g, 88.9 percent yield).

[1394]¹H NMR (toluene-d₈): δ 0.9-1.4 (br m, 24 H), 2.3 (s, 6 H), 2.8 (s,6 H), 3.7 (s, 2 H), 7.0 (br s, 6 H). ¹³C NMR (toluene-d₈): δ22.51, 24.03(br), 28.17, 36.82, 42.67, 123.19, 124.78, 140.71, 145.02 (br). MS(EI):m/z 460.4025 (M-H)⁺, calcd. (M-H)⁺460.4026.

[1395] 2G) Preparation of1,2-Bis(2,6-diisopropylanilide)-1,2-bis(dimethylamido)diborane,dilithium salt.

[1396] 1,2-Bis(2,6-diisopropylanilide)-1,2-bis(dimethylamido)diborane(1.820 g, 3.950 mmol) was stirred in hexane (75 ml) as n-BuLi (7.91mmol, 4.94 ml of 1.6 M solution in hexane) was added dropwise. Thismixture was then allowed to stir overnight. After the reaction periodthe mixture was filtered and the salt washed well with hexane and driedunder vacuum resulting in the isolation of the desired product as awhite powder (1.6878 g, 90.4 percent yield).

[1397]¹H NMR (THF-d₈): δ1.04 (d, ³J_(HH)=6.9 Hz, 6 H), 1.18 (d,³J_(HH)=6.9 Hz, 6 H), 2.45 (s, 12 H), 3.66 (septet, ³J_(HH)=6.9 Hz, 4H), 6.29 (t, ³J_(HH)=7.5 Hz, 2 H), 6.73 (d, ³J_(HH)=7.5 Hz, 4 H). 13CNMR (THF-d₈): 6 24.88, 25.34, 28.00, 40.91, 114.40, 121.95, 137.21,158.76.

[1398] 2H) Preparation ofDichloro-[1,2-Bis(2,6-diisopropylanilide)-1,2-bis(dimethylamido)diborane]titanium.

[1399] 1,2-Bis(2,6-diisopropylanilide)-1,2-bis(dimethylamido)diborane,dilithium salt (0.600 g, 1.27 mmol) in THF (20 ml) was added dropwise toa slurry of TiCl₃(THF)₃ (0.471 g, 1.27 mmol) in THF (50 ml) at 0° C.This mixture was then allowed to stir at room temperature for 45minutes. PbCl₂ (0.177 g, 0.640 mmol) was then added as a solid and themixture allowed to stir for an additional 30 minutes. After the reactionperiod the volatile components were removed and the residue wasextracted and filtered using hexane. Concentration of the hexanefractions and cooling to −10° C. overnight resulted in the formation oforange X-ray quality crystals (0.156 g, 21.3 percent yield). The ORTEPcrystal structure based on X-ray analysis is found in FIG. 1.

[1400]¹H NMR (toluene-d₈): δ 1.23 (d, ³J_(HH)=6.6 Hz, 6 H), 1.45 (d,³J_(HH)=6.6 Hz, 6 H), 2.17 (s, 6 H), 2.76 (s, 6 H), 3.53 (septet,³J_(HH)=6.6 Hz, 4 H), 7.11 (s, 6 H). ¹³C NMR (toluene-d₈): δ 24.94,24.67, 29.48, 39.33, 42.93, 124.08 (br), 17.23, 150.64. MS(EI): m/z578.2789 (M)⁺, calcd. (M)⁺578.2781. Anal. Calcd. For C₂₈H₄₆B₂N₂TiCl₂: C,58.07; H. 8.01; N, 9.67. Found: C, 8.28; H, 8.20; N, 9.42.

Example 3 Dimethyl[1,2-Bis(2,6-diisopropylanilide)-1,2-bis(dimethylamido)diborane]titanium

[1401]Dichloro-[1,2-Bis(2,6-diisopropylanilide)-1,2-bis(dimethylamido)diborane]titanium(Example 2) (0.272 g, 0.470 mmol) was stirred in diethylether (40 ml) asMeMgBr (0.940 mmol, 0.313 ml of 3.0 M solution in diethylether) wasadded dropwise. This mixture was allowed to stir for one hour. After thereaction period the volatiles were removed and the residue extracted andfiltered using hexane. Removal of the hexane resulted in the isolationof the desired product as a dark yellow oil (0.209 g, 82.5 percentyield).

[1402]¹H NMR (C₆D₆): δ 1.05 (s, 6 H), 1.21 (d, ³J_(HH)=6.9 Hz, 16 H),1.32 (d, ³J_(HH)=6.3 Hz, 16 H), 2.19 (s, 6 H), 2.69 (s, 6 H), 3.58 (br,2 H), 7.0-7.2 (m, 6 H). ¹³C NMR (C₆D₆): δ 24.06, 24.83, 29.31, 39.58,42.93, 57.38, 123.97, 125.18, 139.5 (br), 149.45.

Example 4 Dibenzyl[1,2-Bis(2,6-diisopropylanilide)-1,2-bis(dimethylamido)diborane]zirconium

[1403] Zirconium tetrachloride(0.100 g, 0.440 mmol) and zirconiumtetrabenzyl (0.192 g, 0.440 mmol):were stirred together in diethylether(30 ml) for 1 hour.1,2-Bis(2,6-diisopropylanilide)-1,2-bis(dimethylamido)diborane,dilithium salt (Example 2G) (0.400 g, 0.842 mmol) in diethylether (30ml) was then added dropwise and the mixture allowed to stir for 3 hours.After the reaction period the volatiles were removed under vacuum andthe residue extracted and filtered using hexane. The filtrate was thenconcentrated and cooled to −10° C. overnight during which time a whitepowder precipitated. The mixture was again filtered and the volatilecomponents removed resulting in the isolation of the desired product asa yellow oil (0.123 g, 19.8 percent yield).

[1404]¹H NMR (toluene-d₈): δ 1.14 (d, ³J_(HH)=6.6 Hz, 6 H), 1.22 (br, 6H), 1.70 (d, ³J_(HH)=9.0 Hz, 2 H), 1.83 (d, ³J_(HH)=9.6 Hz, 2 H), 2.10(s, 6 H) 2.71 (s, 6 H), 3.0-3.2 (br, 2 H,), 3.3-3.5 (br, 2 H), 6.59 (d,³J_(HH)=7.2 Hz, 4 H), 6.77(t, ³J_(HH)=7.2 Hz, 2 H), 6.9-7.1 (m, 10 H).¹³C NMR (toluene-d₈): δ 23.96 (br), 24.22 (br), 24.36 (br), 25.23 (br),29.47, 3972 43.05, 62.23, 122.70, 123.73 (br), 124.08 (br), 124.33,127.23, 130.82, 139.26 (br), 140.16 (br), 144.90, 144.92, 149.03.

Example 5rac-diisopropylamidoborane-bis-η⁵-(2-methyl4-phenylinden-1-yl)zirconiumη⁴-1,4-diphenyl-1,3-butadiene

[1405]

[1406] 5A) Preparation of Diisopropylaminoboron dichloride.

[1407] To a methylene chloride solution of trichloroborane (1.0 M, 100ml, 0.10 mole) was added dropwise at −78° C. diisopropylamine (13.108ml, 0.100 mole) over a 30 minute period. The solution was allowed tostir for 1 hour, during which a white precipitate formed. The mixturewas allowed to warm to room temperature, and solvent was removed underreduced pressure. The residue was dissolved in 100 ml of drytoluene,trimethylamine (13.94 ml, 9.10 mole) was added and the solutionwas stirred overnight at room temperature. The mixture was filtered, theresidue was washed with 20 ml of toluene. Solvent was removed underreduced pressure from the combined filtrates, and the resulting oil waspurified by vacuum distillation (25-28° C., 13 Pa, 0.1 mm) to give 9.2g(51 percent) of product as a colorless liquid.

[1408]¹H NMR (C₆D₆): δ 0.95 (d, 12 H), 3.63 (broad multiplet, 2 H).

[1409] 5B) Preparation of N,N-diisopropylaminobis(2-methyl-4-phenylindenyl) borane

[1410] To 25 ml THF solution of N,N-diisopropylaminoboron dichloride(0.858 g, 4.72 mmole) at room temperature was added drop wise lithium(2-methyl-4-phenyl)indenide (2.00 g, 9.44 mmole in 20 ml THF). Themixture was stirred for 24 hours. Solvent was removed under reducedpressure. The residue was extracted with toluene (2×50 ml), filteredthrough a medium frit, and solvent was removed under reduced pressure togive a light yellow solid (2.4 g, 97 percent).

[1411] 5C) Preparation ofrac-diisopropylaminoborane-bis-η⁵-(2-methyl4-phenylindenyl)zirconiumη⁴-1,4-diphenyl-1,3-butadiene

[1412] N,N-diisopropylamino bis(2-methyl-4-phenylindenyl) borane (1.20g, 2.3 mmole) was dissolved in 40 ml of toluene, 2.1 equivalents ofpotassium bis(trimethylsilyl) amide (0.964 g, 4.8 mmole) was added andthe resulting mixture was stirred at room temperature for 24 hours.Volatile components were removed under reduced pressure, and theresulting orange solid washed with 10 ml of hexane, filtered and pumpeddry. The dipotassium salt residue (1.3 g, 95 percent, 2.18 mmole) wasredissolved in 25 ml of toluene.(1,4-diphenyl-1,3-butadiene)-bis(trimethylphosphine)zirconium dichloride(1.318 g, 2.18 mmole) was added and the solution stirred for 12 hat roomtemperature. The product mixture was filtered through diatomaceous earthfilter aid and the solvent of the filtrate was removeed under reducedpressure. Further purification was carried out by recrystallization fromhexane to yield 0.85 g (48 percent) of the desired product as a dark redsolid.

[1413]¹H NMR (C₆D₆): δ 7.6(d, 2H); 7.42-7.00, (m, 18 H); 6.9 (d, 2H);6.82 (d, 4H); 5.57 (s, 2H); 4.03, M, 2H); 3.45-3.57 (dd, 2H); 1.8(s,6H);1.28-1.33 (m, 12H).

Example 6 Preparation ofdiisopropylamidoboranebis-(cyclopentadienyl)zirconium dichloride

[1414] 6A) Diisopropylamidoboron dichloride

[1415] To a solution of BCl₃ (17 g, 145 mmol) in CH₂Cl₂ (25 ml) at −78°C. was slowly added diisopropylamine (18.49 ml, 132 mmol). A whiteprecipitate formed during addition. The mixture was warmed to roomtemperature to give a colorless solution. Solvent was removed under highvacuum at room temperature, the residue was then dissolved in benzene(45 ml). Triethylamine (18.8 ml, 134.6 mmol) was added to the solutionat room temperature, the mixture was then stirred overnight at roomtemperature, then filtered to give a red solution. Vacuum distillation(27-28° C., 4 Pa) gave the product (15 g, 57 percent) as a colorlessliquid:

[1416]¹H NMR (500 MHz, CDCl₃) δ 1.26 (d, 12H, J=5.8 Hz), 3.95 (br, 2H,NCH) ¹³C NMR (100 MHz, CDCl₃) δ 22.1, 49.2 (br). ¹¹B NMR (115 MHz,CDCl₃) 29.4. MS (EI, m/e (intensity)): 181 (M+, 5), 166 (43), 124 (61),43 (I 00)

[1417] 6B) Diisopropylamidobis(cyclopentadienyl) borane

[1418] To a solution of the above product (0.39 g, 2.1 mmol) in THF (5ml) at =78° C. was added dropwise a solution of lithiumcyclopentadienide (0.31 g, 2.1 mmol) in THF (10 ml) at −78° C. Themixture was slowly warmed to room temperature and stirred overnight roomtemperature to give a red solution. After solvent removal, the residuewas extracted with pentane (3×), filtered, pentane was then removed togive the product (0.55 g, 100 percent) as an yellow syrup.

[1419]¹³B NMR (115 MHz, C6D,) d 39.8 (major), 30.4 (minor). MS (EI, m/e(intensity)): 241 (M+, 47), 226 (40), 176 (16), 93 (100)

[1420] GC-MS was also recorded on the reaction mixture shortly aftermixing the two reagents at −78° C., from which onlycyclopentadienyldiisopropylboron chloride was detected: MS (EI, m/e(intensity)): 211 (M+, 24), 196 (100), 154 (22).

[1421] 6C) Dilithium diisopropylamidoboryldicyclopentadienide

[1422] To a solution of the above product (0.61 g, 2.53 mmol) in THF (7ml) at −78° C. was added lithium diisopropylamide (5.57 mmol, preparedin situ from diisopropylamine (0.780 ml, 5.57 mmol) and BuLi (2.50 M,2.23 ml, 5.57 mmol). The mixture was warmed to room temperature andstirred for 2 hr. Solvent was then removed, residue was washed withpentane to give the product (0.58 g, 91 percent) as a white solid:

[1423]¹H NMR (360 MHz, THF-d₈) d 1.24 (d, 12H, J=6.8 Hz, NCHCH₃), 4.54(m, 2H, NCH), 5.74 (t, 4H, J=2.4 Hz), 5.83 (t, 4H, J=2.4 Hz)

[1424]¹³C NMR (100 MHz, THF-d₈) d 23.9 (NCHCH₃), 25.9 (NCHCH₃), 49.3(NCH), 104.4, 111.9

[1425]¹¹B NMR (115 MHz, THF-d₈) d 44.6

[1426] 6D) Diisopropylamidoboranebis(cyclopentadienyl)zirconiumdichloride

[1427] To a solution of diisopropylamidobis(cyclopentadienyl)borane(0.71 g, 2.95 mmol) in Et₂O (15 ml) at −78° C. was added lithiumdiisopropylamide (6.93 mmol). The mixture was stirred for 2 hr at roomtemperature to give a slightly turbid solution. The solution was thenadded to a suspension of ZrCl₄ (0.69 g, 2.95 mmol) in Et₂O (15 ml) at−78° C. The resulting mixture was stirred overnight at room temperatureto give an yellowish suspension. Solvent was partially removed and theresidue concentrated and cooled to −78° C. to give the product (0.50 g,38 percent) as colorless crystals.

[1428]¹H NMR (400 MHz, CDCl₃) d 1.32 (d, 12H, J=7.0 Hz), 2.92 (m, 2H),5.65 (t, 4H, J=2.4 Hz), 6.80 (t, 4H, J=2.4 Hz). ¹³C NMR (100 MHz, CDCl₃)d 24.6, 49.6, 111.4, 125.7. ¹³B NMR (115 MHz, CDCl₃) 5 37.6. HRMS (EI),calculated for C₁₆H₂₂BNC₁₂Zr: 399.0269, found: 399.0272.

Example 7 Preparation ofmeso-diisopropylamidoboranebis(inden-1-yl)zirconium dichloride

[1429] 7A) Diisopropylamidobis(inden-1-yl)borane

[1430] To a solution of diisopropylamidoboron dichloride (Example, 3,step A)) (1.10 g, 6.0 mmol) in THF (10 ml) at −78° C. was added dropwisea solution of lithium indenide (1.50 g, 12.3 mmol) in THF (40 ml) at−78° C. The mixture was slowly warmed to room temperature and stirredovernight at room temperature to give a red solution. After solventremoval, the residue was extracted with CH₂Cl₂ (3×), filtered and thesolvent removed to give the desired product (2.12 g, 100 percent) as awhite solid:

[1431]¹¹B NMR (115 MHz, C₆D,) d 41.4. MS (EI, m/e (intensity)): 341 (M+,8), 226 (100). HRMS (EI), calculated for C₂₄H₂₈BN C₂₄H₂₈BN: 341.2315,found: 341.2310

[1432] 7B) Meso-Diisopropylamidoboranebis(inden-1-yl)zirconiumdichloride

[1433] To a suspension of the above product (0.39 g, 1.41 mmol) in Et₂O(10 ml) at −78° C. was added lithium diisopropylamide (in situ preparedfrom iPr₂NH (2.62 mmol) and BuLi (2.50 M, 2.62 mmol). The mixture wasstirred overnight room temperature to give an orange suspension. Solventwas removed and the residue extracted with toluene, and filtered.Toluene was then removed to give an orange solid composed of a mixtureof the two stereoisomers (rac/meso, ca. 6:4). Repeated recrystallization(3×) from toluene at −78° C. gave the pure meso isomer (0.08 g, 14percent) as an orange solid. M.p.=250-254° C. (dec.)

[1434]¹HNMR (500 MHz, CDCl₃) 1.54(d, 6H, J=6.6 Hz), 1.57 (d, 6H, J=6.8Hz), 4.27 (m, 2H, NCH), 5.91 (d, 2H, J3.0 Hz), 6.9 (m, 4H), 7.17 (t, 2H,J=7.6 Hz), 7.31 (dd, 2H, J=8.3, 3.6 Hz), 7.53 (d, 2H, J=8.6 Hz). ¹³C NMR(75 MHz, CDCl₃) d 24.7, 25.0 (NCHCH₃), 49.7, 100.2 (BC), 115.7, 117.2,125.2, 125.3, 125.6, 125.9, 1.26.5, 131.4. ¹¹B NMR (115 MHz, CDCl₃) 839.5. HRMS (EI), calculated for C₂₄H₂₆BNC₁₂Zr: 499.0582, found,499.0606. MS (EI, m/e (intensity)): 501 (M+, 20), 458 (7), 341 (18), 226(93), 143 (80), 115 (99)

Example 8 Preparation ofrac-diisopropylamidoboranebis(inden-1-yl)zirconium bis(dimethylamide)

[1435] To a mixture of diisopropylamidobis(inden-1-yl)borane (Example 4,step A)) (1.01 g, 2.96 mmol) and Zr(NMe₂)₄ (0.79 g, 0.96 mmol) was addedtoluene (15 ml). The resulting solution was heated to 65° C. and stirredfor 2 hr to give a bright red solution. The product consisted of twoisomers with a ratio of 6.7:1. The solution was filtered, concentrated,and cooled to −78° C. to give the pure rac isomer (0.50 g, 33 percent)as red crystals. The structure was confirmed by X-ray diffractionanalysis on single crystals grown from toluene/hexane at −20° C.M.p.=220° C. (dec.).

[1436]¹H NMR (500 MHz, C₆D₆) d 1.20 (d, 6H, J=6.8 Hz), 1.27 (d, 6H,J=6.6 Hz), 2.61 (s, 12H), 3.86 (in, 2H), 6.04 (d, 2H, J=2.9 Hz), 6.74(m, 4H), 7.00 (t, 2H, J=7.6 Hz), 7.37 (dd, 2H, J=8.5, 0.9 Hz), 7.52 (d,2H, J=8.5 Hz). ¹³C NMR (90 MHz, C₆D₆) 5 24.6, 24.9, 47.9 (NCH₃), 49.6,1105.6, 112.4, 123.1, 123.2, 124.0, 124.2, 126.3, 129.1. ¹¹B NMR (115MHz, C₆D₆) d 40.8. HRMS (EI), calculated for C₂₈H₃₈BN₃Zr: 517.2206,found, 517.2217. MS (EI, m/e (intensity)): 517 (M+, 20), 471 (45), 429(100), 330 (24),226 (70)

Example 9 Rac-Diisopropylamidoboranebis(inden-1-yl)zirconium dichloride

[1437] To a solution ofrac-diisopropylamidoboranebis(inden-1-yl)zirconium bis(dimethylamide)(0.50 g, 0.96 mmol) in toluene (35 ml) at room temperature was addedtrimethylsilyl chloride (2.0 ml, 15.76 mmol). The solution was stirredfor 8 h at room temperature to give an orange suspension. Solvent wasremoved, residue was washed with pentane (2×) to give the desiredproduct (0.40 g, 83 percent) as an orange powder. Single crystalssuitable for X-ray structural analysis were grown from mixed solvents ofCH₂Cl₂ and hexane at −20° C. M.p.=242° C. (dec.).

[1438]¹H NMR (500 MHz, CDCl₃) d 1.50 (d, 6H, J=6.8 Hz), 1.55 (d, 6H,J=6.6 Hz), 4.24 (heptet, 2H, J=7.7 Hz), 5.79 (d, 2H, J=3.0 Hz), 6.80(dd, 2H, J=3.2, 0.7 Hz), 7.07 (t, 2H, J=7.6 Hz), 7.28 (dd, 2H, J=7.0 0.7Hz), 7.3 8 (t, 2H, J=8.0 Hz), 7.58 9d, 2H, J=8.8 Hz). ¹³C NMR (75 MHz,CDCl₃) d 24.7, 25.0,49.6,98.4 (BC), 113.1, 114.1, 122.0, 123.0, 125.8,126.4, 127.2, 131.9. ¹¹B NMR (115 MHz, CDCl₃) d 39.2. HRMS (EI),calculated for C₂₄H₂₆BNCl₂Zr: 499.0582, found, 499.0606. MS (EI, m/e(intensity)): 501 (M+, 20), 458 (7), 341 (18), 226 (93), 143 (80), 115(99). Anal. Calculated for C₂₄H₂₆BNCl₂Zr: C, 57.48; H, 5.19; N, 2.79.Found: C, 57.46; H, 5.32; N, 2.68.

Example 10 Preparation ofrac-(diisopropylamidoborane)bis(tetrahydroinden-1-yl)zirconiumdichloride

[1439] A solution of diisopropylamidoboranebis(inden-1-yl)zirconiumdichloride (Example 6) (0.16 g, 0.32 mmol) in CH₂Cl₂ (7 ml) was added toan autoclave reactor containing PtO₂ (0.0105 g). The mixture was flushedfour times with H₂ (200 psi, 1.4 MPa), then charged with H₂ (1500 psi,10.4 MPa) and stirred for 15 h at room temperature to give a greenishsuspension. CH₂Cl₂ (25 ml) was added the mixture which was thenfiltered. Solvent was removed under reduced pressure and the residue waswashed with pentane (2×) to givediisopropylamidoboranebis(tetrahydro-inden-1-yl)zirconium dichlodride(0.15 g, 92 percent) as a slightly greenish solid.

[1440]¹H NMR (400 MHz, C₆D₆) d 1.06 (d, 12H, J=6.6 Hz), 1.33 (m, 2H),1.47 (m, 2H), 1.92 (m, 4H), 2.05 (t, 1H, J=4.8 Hz), 2.09 (d, 1H, J=5.0Hz), 2.34 (m, 2H), 2.53 (t, 1H, J=5.3 Hz), 2.156 (t, 1H, J=5.0 Hz), 3.20(m, 2H), 3.60 (hept, 2H, J=6.6 Hz), 5.01 (d, 2H, J=2.9 Hz), 6.53 (d, 2H,J=2.6 Hz). ¹³C NMR (100 MHz, C₆D₆) d 23.0, 23.6, 24.4, 24.7, 24.8, 27.0,49.6, 109.7, 121.6, 124.2, 136.1. ¹¹B NMR (115 MHz, C₆D₆) d 39.2 ppm.HRMS (EI) Calculated for C₂₄H₃₄ ¹¹BNCl₂Zr 507.1208, found 507.1198

Example 11 Preparation of rac-N,N-diisopropylamidoborane-bis-η⁵-(2-methyl-4-naphthyl indenyl) zirconium η⁴-1,4-diphenyl-1,3-butadiene.

[1441]

[1442] 11A) Preparation of potassium (2-methyl-4-naphthyl) indenide

[1443] 2-Methyl-4-naphthylindene (1.00 g, 3.27 mmole) was dissolved in20 ml of toluene, potassium bis(trimethylsilyl)amide (1.05 equivalent,3.43 mmole, 0.684 g) was added and the reaction mixture was stirred atroom temperature for 24 hours, during which a yellow solid precipitated.Hexane was added (20 ml) and the mixture was stirred for 2 h. The solidproduct was isolated by vacuum filtration through a medium porosityfrit. The solid was pumped dry giving 1.10 g, 98 percent of the desiredproduct.

[1444] 11B) Preparation of N,N-diisopropylaminobis(2-methyl-4-naphthylindenyl) borane

[1445] To a solution of N,N-diisopropylaminoboron dichloride (0.309 g,1.70 mmole) in 25 ml of THF at room temperature was slowly addeddropwise a 10 ml THF solution of potassium (2-methyl-4-naphthyl)indenide (1.00 g, 3.40 mmole). The mixture was stirred for 24 hours atroom temperature, solvent was removed, and the residue was extractedwith toluene (2×25 ml). The combined extracts were filtered through amedium frit, and solvent was removed under reduced pressure to give alight yellow solid (1.0 g, 95 percent).

[1446] 11C) Preparation of rac-N,N-diisopropylaminoborane-bis-η⁵-(2-methyl-4-naphthyl indenyl) zirconium η⁴-1,4-diphenyl-1,3-butadiene.

[1447] N,N-diisopropylamino bis(2-methyl-4-naphthylindenyl) borane(0.860 g, 1.38 mmole) was dissolved in 20 ml of toluene, 2.05equivalents of potassium bis(trimethylsilyl)amide (0.566 g, 2.84 mmole)was added and the reaction mixture was stirred at room temperature for24 hours. Volatile components were removed under reduced pressure, andthe residue was redissolved in 25 ml of toluene. While stirring at roomtemperature,(1,4-diphenyl-1,3-butadiene)bis(trimethylphosphine)-zirconium dichloride(0.835 g, 1.38, mmol) was added and the solution was stirred for 12 h atroom temperature. The product mixture was filtered through diatomaceousearth filter aid and the solvent of the filtrate was removed underreduced pressure. Further purification was carried out byrecrystallization from hexane to yield 0.27 g (21 percent) of thedesired product as a dark red solid.

[1448]¹H NMR (C₆D₆): δ7.75−7.00, (mm, 30 H), 4.82 (s, 2H); 3.85-3.95(m,2H); 3.62-3.70 (dd, 2H); 1.82-1.9 (dd, 2H) 1.6 (s, 6H); 1.10-1.33 (m,12H).

Example 12rac-1,2-bis(dimethylamidodiborane)bis(2-methyl-4-phenylinden-1-yl)zirconiumη⁴-1,4-diphenyl-1,3-butadiene

[1449]

[1450] 12A) Preparation of1,2-Bis(2-methyl-4-phenylinden-1-yl)-1,2-bis(dimethylamido)-diborane

[1451] Bis(dimethylamido)diborondichloride (0.500 g, 2.77 mmol) indiethylether (10 ml) was added dropwise to a solution of2-methyl-4-phenylindene, lithium salt (1.407 g, 11.07 mmol) indiethylether (50 ml) at 0° C. This mixture was stirred overnight at roomtemperature and the volatiles were removed. The residue was extractedusing CH₂Cl₂. Filtration and removal of the CH₂Cl₂ resulted in theisolation of a the desired product as a pale yellow solid (0.902 g, 62.6percent yield).

[1452] 12B) Preparation of1,2-Bis(dimethylamido)-1,2-bis(2-methyl-4-phenylindene)diborane,dipotassium salt.

[1453] 1,2-Bis(dimethylamido)-1,2-bis(2-methyl-4-phenylindene)diborane(0.791 g, 1.52 mmol). and KN(TMS)₂ (0.607 g, 3.04 mmol) were stirredtogether in toluene (50 ml) overnight. The reaction mixture was thenrefluxed for one hour, cooled to room temperature, and dried undervacuum. The residue was then slurried in hexane and filtered and thegold microcrystalline solid dried under vacuum (0.881 g, 97.1 percentyield).

[1454] 12B) Preparation ofrac-[1,2-Bis(dimethylamido)-1,2-bis(2-methyl-4-phenylindene)diborane]zirconium(trans,trans-1,4-diphenyl-1,3-butadiene)

[1455] 1,2-Bis(dimethylamido)-1,2-bis(2-methyl-4-phenylindene)-diborane,dipotassiium salt (0.808 g, 1.35 mmol) was added slowly as a solid to asolution of (1,4-diphenylbutadiene)ZrCl₂(PEt₃)₂ (0.819 g, 1.35 mmol) intoluene (75 ml). This mixture was allowed to stir overnight. After thereaction period the mixture was filtered and the volatiles removedresulting in the isolation of a deep red residue. The residue was thenslurried in cold hexane, filtered, and dried under vacuum resulting inthe isolation of the desired product as a dark red microcrystallinesolid (0.501 g, 45.3 percent yield).

[1456]¹H NMR (C₆D₆): δ 1.1-1.2 (m, 2 H), 2.02 (s, 6 H), 2.66 (s, 6H),2.90 (s, 6 H), 3.3-3.4 (m, 2 H), 5.28 (s, 2 H), 6.82 (d, ³J_(HH)=6.6 Hz,2 H), 6.9-7.3 (m, 14 H), 7.53 (d, ³J_(HH)=8.4 Hz, 2 H). ¹³C NMR (C₆D₆):δ15.10, 42.17, 44.36, 86.78, 93.34, 106.54, 119.17, 123.12, 123.39,123.71, 124.26, 127.88, 128.51, 128.90, 129.34, 135.76, 140.85, 145.80.

Example 13rac-diisopropylamidoborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)hafniumη⁴-1,4-diphenyl-1,3-butadiene

[1457]

[1458] Hafnium tetrachloride (0.375 g, 1.17 mmol) was slurried into 40ml of toluene. To this slurry were added trimethylphosphine (0.346 ml,2.34 mmol, via syringe), Li powder (Aldrich, low sodium, 0.081 g, 11.7mmol), and 1,4-diphenyl-1,3-butadiene (0.242 g, 1.17 mmol). The reactionmixture was stirred overnight at room temperature then filtered using amedium porosity frit and diatomaceous earth pad to remove the unreactedLi metal. To the filtrate was added dipotassiumdiisopropylamidobis(1-(2-methyl-4-phenylindenide))borane,K₂[^(i)Pr₂NB(2-Me-4-Ph-indenide)₂], (0.700 g, 1.17 mmol) using 10 ml oftoluene to aid in the transfer. The reaction mixture was stirred for 1hour at room temperature. The toluene was removed under reduced pressureand the reaction product was extracted with hexane (twice) and filtered(medium porosity frit with diatomaceous earth pad). Additional productwas obtained by extracting the salt byproduct using toluene andrefiltering using a medium porosity frit and diatomaceous earth pad.

[1459]¹H NMR spectroscopic analysis indicated that the desiredrac-^(i)Pr₂NB(2-Me-4-Ph-inden-1-yl)₂Hf(1,4-diphenyl-1,3-butadiene)isomer was largely insoluble in hexane and that the undesiredmeso-isomer could be separated by repeated extraction with hexane. Finalisolation and purification ofrac-^(i)Pr₂NB(2-Me-4-Ph-inden-1-yl)₂Hf(1,4-diphenyl-1,3-butadiene) wasaccomplished by soxhlet extraction using hexane. After the hexaneextract becomes colorless the thimble was removed and dried, yielding0.042 g of purerac-^(i)Pr₂NB(2-Me-4-Ph-inden-1-yl)₂Hf(1,4-diphenyl-1,3-butadiene) asdetermined by ¹H and ¹³C NMR spectroscopic analysis.

[1460]¹H NMR (C₆D₆): δ 7.6(d, 2H); 7.42-7.00, (m, 18 H); 6.9 (d, 2H);6.82 (d, 4H); 5.57 (s, 2H); 4.03, m, 2H); 3.45-3.57 (dd, 2H); 1.8(s,6H);1.28-1.33 (m, 12H).

Example 14rac-diisopropylamidoborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconiumη⁴-1,4-diphenyl-1,3-butadiene

[1461]

[1462] In a glove box,diisopropylamidobis(2-methyl-4-phenylinden-1-yl)borane (0.125 g, 0.240mmole) was dissolved in 20 ml of dry THF, and 2 equivalents of potassiumbis(trimethylsilyl)amide (0.500 molar solution, 0.960 ml, 0.480 mmole)was added dropwise over 10 minute period at room temperature, afterwhich the solution was stirred for 4 hours. Volatile components wereremoved under reduced pressure and the remaining solids were redissolvedin 25 ml of toluene. While stirring at room temperature,(1,4-diphenyl-1,3-butadiene)bis(trimethylphosphine)zirconium dichloride(0.145 g, 0.240 mmole) was added and the resulting solution was stirredfor 4 hours. The product was recovered by filtering the mixture throughdiatomaceous earth and removing the solvent of the filtrate underreduced pressure. Further purification was carried out byrecrystallization from hexane to yield the product as a dark red solid.

Example 15 Preparation of rac-{Pr₂NC(N^(i)Pr)₂}borane-bis-η⁵-(2-methyl-4-phenylindenyl) zirconium η⁴-1,4-diphenyl-1,3-butadiene.

[1463]

[1464] 15A) Preparation of ^(i)Pr₂NC(N^(i)Pr)₂}boron dichloride.

[1465] Diisopropylcarbodiimide (1.178 g, 9.33 mmole) was dissolved in 20ml of toluene, cooled to 0° C., and solid lithium diisopropylamide (1.00g, 9.33 mmole) was added slowly to the solution over a 5 minute period.The solution was was allowed to warm to room temperature while stirringfor 3 hours. This solution was subsequently added dropwise over a 30minute period to a 1 molar heptane solution (0° C.) of boron trichloride(9.33 ml, 9.33 mmole) and allowed to warm to room temperature overnight.The solution was filtered, and solvents were removed under reducedpressure to yield 2.3 g (97 percent) of light yellow oil.

[1466]¹H NMR (C₆D₆): δ 3.6-3.4 (m, 2H); 3.4−3.25 (septet, 2H); 1.43 (d,12H); 0.8 (d, 12 H).

[1467] 15B) Preparation of bis(2-methyl-4-phenylindenyl){^(i)Pr₂NC(N^(i)Pr)₂)borane

[1468]^(i)Pr₂NC(N^(i)Pr)₂}boron dichloride (0.30 g, 0.97 mmole) wasdissolved in 30 ml of THF, and potassium (2-methyl-4-phenyl)indenide(0.476 g, 1.95 mmole) was added. The mixture was stirred for 24 hours atroom temperature, followed by heating at reflux for 4 hours. The productmixture was allowed to cool to room temperature, and solvent was removedunder reduced pressure. The residue was extracted with toluene (2×50ml), filtered through a medium frit, and solvent was removed underreduced pressure to give a light yellow solid (0.533 g, 85 percent).

[1469] 15C) Preparation of rac-{^(i)Pr₂NC(N^(Pr)) ₂}borane -bis-η⁵-(2-methyl-4-naphthyl indenyl) zirconium η⁴-1,4-diphenyl-1,3-butadiene.

[1470] Bis(2-methyl-4-phenylindenyl) {^(i)Pr₂NC(N^(i)Pr)₂}borane (0.533g, 0.82 mmole) was dissolved in 20 ml of toluene, 2.00 equivalents ofpotassium bis(trimethylsilyl)amide (0.0.328 g, 1.65 mmole) was added andthe reaction mixture was stirred at room temperature for 24 hours.Volatile components were removed under reduced pressure, and the residuewas washed with 2×25 mL of hexane. Volatile components were removedunder reduced pressure to yield 0.382 9 (64 percent) of the orange soliddipotassium salt. A portion of this solid (0.100 g, 0.14 mmole) wasdissolved in 15 mL of toluene. While stirring at room temperature,(1,4-diphenyl-1,3-butadiene)bis(trimethylphosphine)zirconium dichloride(0.084 g, 0.14 mmole) was added and the solution was stirred for 12 h atroom temperature. The product mixture was filtered through diatomaceousearth filter aid and the solvent of the filtrate was removed underreduced pressure to give 0.115 g (88 percent) of crude product whichexisted as a rac/meso mixture. Further purification was carried out byrecrystallization from hexanes to yield 0.015 g (12percent) ofrac-product as a dark red solid.

[1471]¹H NMR (C₆D₆): δ 7.6-6.7, (mm, 26 H); 5.55 (s, 2H); 4.05−3.90(m,2H); 3.5 (dd, 2H); 2.7-2.4 (m, 2H); 1.78 (s, 6H); 1.55 (dd, 2H); 1.25(m, 12 H); 0.95 (m, 12H).

Example 16rac-dimethylamidoborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconiumη⁴-1,4-diphenyl-1,3-butadiene

[1472]

[1473] 16A) Preparation of Dimethylamidodibromoborane

[1474] B(NMe₂)₃ was added to BBr₃ dropwise. The reaction was immediateand exothermic. This mixture was allowed to stir for 2 hours at whichtime NMR analysis showed the reaction to be essentially quantitative andcomplete (22.510 g, 99.9 percent yield).

[1475]¹H NMR (C₆D₆): δ 2.31 (6 H). ¹³C NMR (C₆D₆): δ 41.45.

[1476] 16B) Preparation ofDimethylamido-bis(2-methyl-4-phenylindenyl)borane.

[1477] A solution of dimethyamidodibromoborane (0.511 g, 2.38 mmol) intoluene (10 ml) was cooled to 0° C. and diethylether (2 equivelents)added. This mixture was then added dropwise to a solution of2-methyl-4-phenylindene, lithium salt (1.011 g, 4.76 mmol) in THF (50ml) at 0° C. This mixture was then allowed to stir for overnight at roomtemperature. After the reaction period the volatile components wereremoved and the residue extracted and filtered using hexane. Removal ofthe hexane resulted in the isolation of a yellow oil (1.103 g, 99.9percent yield).

[1478] 16C) Preparation ofDimethylamido-bis(2-methyl-4-phenylindenyl)borane, dipotassium salt.

[1479] Dimethylamido-bis(2-methyl-4-phenylindenyl)borane (1.010 g, 2.17mmol) and KN(TMS)₂ (0.866 g, 4.34 mmol) were stirred together in toluene(50 ml)overnight. The reaction mixture was then refluxed for one hour,cooled to room temperature, and dried under vacuum. The residue was thenslurried in hexane and filtered and the orange microcrystalline soliddried under vacuum (1.246 g,>100% yield due to residual solvent stillpresent as observed by NMR).

[1480] 16D) Preparation ofrac-[Dimethylamido-bis(2-methyl-4-phenylindene)borane]-zirconium(trans,trans-1,4-diphenyl-1,3-butadiene).

[1481] Dimethylamido-bis(2-methyl-4-phenyl-lindenyl)borane, dipotassiumsalt (1.246 g, 2.30 mmol) was added slowly as a solid to a solution of(1,4-diphenylbutadiene)ZrCl₂(PEt₃)₂ (1.391, 2.30 mmol) in toluene (75ml) and allowed to stir overnight. After the reaction period the mixturewas filtered and the volatiles removed resulting in the isolation of adark residue. This residue was slurried in hexane and filtered. Redcrystals grew over a 2-hour period of time from the sitting hexanefiltrate (0.222 g). The solid on the frit was washed through the fritusing toluene and a second crop of crystals was grown from this mixtureby allowing the solution to slowly concentrate over a period of one weekby slow evaporation of the toluene (0.100 g). Combining the crystalsobtained resulted in the isolation of a total of 0.322 g (18.4 percentyield) of highly pure product.

[1482]¹H NMR (C₆D₆): δ 1.71 (s, 3 H), 1.7-1.8 (m, 2 H), 2.89 (s, 3 H),3.4-3.5 (m, 2 H), 5.52 (s, 2 H), 6.76 (d, ³J_(HH)=7.2 Hz, 4 H), 6.8-7.4(m, 12 H), 7.43 (d,³J_(HH)=8.4 Hz, 2 H). ¹³C NMR (C₆D₆): δ 15.95, 39.52,85.43, 90.93, 104.13, 117.32, 12.49, 121.65, 1122.3 (br), 123.32,124.19, 124.32, 127.81, 127.83, 128.68, 128.74, 128.81, 136.06, 140.55,143.86. MS(EI): m/z 759.2635 (M-H)⁺, calcd. (M-H)⁺759.2610.

Example 17bis(trimethylsilyl)amido(η-fluoren-9-yl)(η-cyclopentadienyl)borane-zirconiumdichloride.

[1483] 17A) Preparation of bistrimethylsilylamido(9-fluorenyl)boronchloride

[1484] n-Butyllithium (2.5 M hexane, 4.20 ml, 10.50 mmol) was added to asolution of fluorene (1.66 g, 10.00 mmol) in THF (15 ml) at −78° C. Theresulting mixture was slowly warmed up and stirred at room temperaturefor 5 h to give a red solution. The solution was cooled to −78° C. andadded dropwise to a solution of bis(trimethylsilyl)amidoboron dichloride(TMS)₂NBCl₂ (2.42 g, 10.00 mmol) in THF (25 ml) at −78° C. to give alight yellow solution. The solution was stirred overnight at roomtemperature. Volatile components were removed, and the residue wasextracted with pentane and filtered. The pentane was removed to give thedesired product (3.70 g, 100 percent yield) as a white solid.

[1485]¹H NMR (400 MHz, CDCl₃): δ 0.45 (s, 18H), 4.41 (s, 1H), 7.34 (dt,2H, J=7.4, 1.1 Hz), 7.42 (t, 2H, J=7.3 Hz), 7.49 (d, 2H, J=7.6 Hz), 7.87(d, 2H, J=7.4 Hz). ¹³C NMR (100 MHz, CDCl₃) δ 4.6, 121.0, 125.4, 127.2,127.3, 143.0, 145.9. ¹¹B NMR (115.5 MHz, CDCl₃,) δ 46.6.

[1486] 17B) Preparation ofbis(trimethylsilyl)amido(9-fluorenyl)(cyclopentadienyl)borane

[1487] A solution of CpNa/THF (0.24 g, 2.40 mmol) in THF (15 ml) at −78°C. was added dropwise to a solution ofbistrimethylsilyamido(9-fluorenyl)boron chloride (0.89 g, 2.40 mmol) THF(15 ml) at −78° C. The resulting yellow solution was slowly warmed toroom temperature with stirring and stirred over night. Volatilecomponents were removed under reduced pressure, and the residue wasextracted with pentane and filtered. The pentane solution wasconcentrated and cooled to −78° C. to give the desired product (0.57 g,59.percent) as a white solid.

[1488]¹H NMR (400 MHz,C₆D₆): δ 0.20 (s, 18 H), 1.71 (t, 2H, J=1.4 Hz),4.33 (s, 1 H), 5.93 (m, 1 H), 6.13 (m, 1 H), 6.69 (dd, 1 H, J=14, 1.5Hz), 7.09 (dt, 2H, J=7.2, 1.5 Hz), 7.19 (dt, 2 H, J=7.4, 1.7 Hz), 7.46(dd, 2H, J=7.4, 1.1 Hz), 7.70 (dd, 2H, J=7.6, 0.8 Hz) ¹³C NMR (100 MHz,C₆D₆,) δ 5.1, 43.4, 120.6, 125.8,126.7, 127.2, 132.2, 139.5, 142.9,143.1, 147.4. ¹¹B NMR (115.5 MHz, C₆D₆) δ 51.6. HRMS (EI) calculated forC₂₃H₂₉BNSi, (M-CH₃), 386.1932; found, 386.1945.

[1489] 17C))bis(trimethylsilyl)amidoborane(η-cyclopentadienyl)(η-fluoren-9-yl)zirconiumdichloride

[1490] A solution of lithium diisopropylamide (prepared in situ fromiPr₂NH (0.54 ml, 3.84 mmol) and BuLi (2.5 M hexane, 1.61 mil, 4.03mmol)) in THF (10 ml) was added to a solution ofbis(trimethylsilyl)amido(9-fluorenyl)(cyclopentadienyl)borane(0.77 g,1.92 mmol) in THF (10 ml) at −78° C. The resulting mixture was slowlywarmed to room temperature and stirred overnight to give a dark redsolution. Volatile components were removed to give an orange solid whichwas then dissolved in toluene (15 ml). The toluene solution was added toa suspension of ZrCl₄ (0.40 g, 1.9 mmol) in toluene (8 ml) at −78° C.The mixture was warmed to room temperature and stirred overnight to givea dark red suspension. Volatile components were removed under reducedpressure, and the residue was extracted with toluene and then filtered.The volatile components were removed under reduced pressure, and theresidue was washed with pentane (3×) to give the product as red solid.

[1491] mp=252-254 (dec.). ¹H NMR (400 MHz, CDCl₃): δ 0.26 (s, 9H), 0.50(s, 9H), 5.44 (t, 2H, J=2.4 Hz), 6.45 (t, 2H, J=2.4 Hz), 7.19 (d, 2H,J=8.4 Hz), 7.31 (t, 2H, J=7.5 Hz), 7.62 (t, 2H, J=7.8 Hz), 8.12 (d, 2H,J=8.4 Hz). ¹³C NMR (75 MHz, CDCl₃) δ4.8, 5.9, 105.3, 121.4, 122.9,124.4, 125.4, 125.7, 129.1, 143,0. ¹¹B NMR (115.5 MHz, CDCl₃) δ 48.2.HRMS (EI) calculated for C₂₄H₃₀BNSi₂Cl₂Zr: 559.0434; found, 559.0443.

Example 18diisopropylamidoborane(η-cyclopentadienyl)(η-fluoren-9-yl)zirconiumdichloride.

[1492] 18A) Preparation of Diisopropylamido(9-fluorenyl)boron chloride

[1493] The reaction conditions of Example 17A) were substantiallyrepeated excepting that diisopropylamidodichloroboron was used in placeof bis(trimethylsilyl)amido-dichloroboron. At the end of the reaction,solvent was removed, residue was extracted with CH₂Cl₂ and filtered.Volatile components were removed to give the product (0.91 g, 98percent) as a yellowish solid.

[1494]¹H NMR (400 MHz, CDCl₃): δ 1.36 (br, 6H), 1.79 (br, 6H), 4.41 (br,1H), 7.35 (t, 2H, J=7.7 Hz), 7.42 (t, 2H, J=7.5 Hz), 7.50 (br, d, 2H,J=4.7 Hz), 7.88 (d, 2H, J=7.3 Hz). ¹³C NMR (100 MHz, CDCl₃) δ 24.5 (br),43.2 (br), 48.5 (br), 120.2, 124.4, 126.4, 126.9, 141.1 (br), 146.9. ¹¹BNMR (115.5 MHz, CDCl₃) δ 37.2. HRMS (EI) Calculated for C₁₉H₂₃BNCl,311.1612; found, 311.1613.

[1495] 18B) Diisopropylamido(cyclopentadienyl)(9-fluorenyl)borane

[1496] The reaction conditions of Example 17B were substantiallyrepeated excepting that diisopropylamido(9-fluorenyl)boron was used inplace of bis(trimethylsilyl)amido(9-fluorenyl)boron chloride. Reactionof CpNa/THF (0.96 g, 9.60 mmol) and diisopropylamido(9-fluorenyl)boronchloride (2.98 g, 10.00 mmol) gave a reaction mixture which wasextracted with hexane and flittered. Volatiles were removed to give theproduct (2.11 g, 62 percent) as a yellow solid.

[1497] HRMS (EI), Calculated for C₂₄H₂₈BN, 341.2315, found, 341.2329.

[1498] 18C) Preparation ofdiisopropylamidoborane(η-cyclopentadienyl)(η-fluoren-9-yl)zirconiumdichloride.

[1499] The reaction conditions of Example 17C) were substantiallyrepeated excepting that diisopropylamido(9-fluorenyl)boron (1,39 g, 4.08mmol) was used in place of bis(trimethylsilyl)amido(9-fluorenyl)boron.The crude reaction mixture from this reaction was extracted with tolueneand filtered. The solution was concentrated, pentane was added andcooled to −78° C. to give the product (0.75 g, 36 percent yield) as ared solid.

[1500] mp=280-282° C. ¹H NMR (500 MHz. C₆D₆): δ 1.01 (d, 6H, J=6.6 Hz),1.22 (d, 6H, J=6.9 Hz), 3.67 (pent, 1H, J=6.6 Hz), 3.80 (pent, 1H, J=6.6Hz), 5.30 (t, 2H, J=2.4 Hz), 6.38 (t, 2H, J=2.4 Hz), 7.05 (d, 2H, J=8.1Hz), 7.12 (t, 2H, J=7.5 Hz), 7.46 (t. 2H, J=7.5 Hz), 7.92 (d, 2H, J=8.5Hz). ¹³C NNIR (90 MHz, CDC13) δ24.2, 25.4, 49.1, 49.8, 106.9, 122.2,123.2, 125.4, 125.8, 129.0, 147.9, 157.1. ¹¹B NMR (115.5 MHz, C6D6) δ39.4. EA, calculated for C₂₄H₂₈BNZrCl₂: C, 57.25, H, 5.57, N, 2.78.Found: C, 55.44; H, 5.30; N, 2.62.

Example 19 bis(trimethylsilyl)amidoborane bis(1-inden-1-yl)zirconiumbis(dimethylamide)

[1501] Bis(trimethylsilyl)amidoboronbis(inden-1-yl) was prepared byreacting lithium indenide (0.50 g, 4.10 mmol) andbis(trimethylsilyl)amidoboron dichloride, (0.48 g, 2.00 mmol) in THF togive the product (0.75, g, 94 percent) as a yellowish solid.

[1502]¹H NMR (400 MHz, C₆D₆, major isomer): δ 0.32 (s, 18H), 3.64 (s,2H), 6.08 (dd, 2H, J=5.5, 1.8. Hz), 6.48 (dd, 2H, J=5.2 Hz), 6.82 (d.,2H, J=7.3 Hz), 0.93 (dt, 2H, J=7.1, 1.2 Hz), 7.20 (m, 4H). ¹¹B NMR(115.5 MHz, C₆D₆) δ 56.8. HRMS (EI) calculated for C₂₄H₃₂BNSi₂,401.2166; found, 401.2182. EA, Calculated for C₂₄H₃₂BNSi₂, C, 71.82; H,7.98; N, 3.49. Found: C, 70.06; H, 8.06; N, 3.36.

[1503] The bis(trimethylsilyl)amidoboron bis(inden-1-yl) (0.27 g, 0.67mmol) and Zr(NMe₂)₄ (0.18 g, 0.67 mmol) were then combined in toluene(10 ml) 2 hours at 65° C. to give a red solution. Volatile componentswere removed under reduced pressure to afford the product as a red foam.

[1504]¹H NMR (400 MHz, C₆D₆): δ 0.26 (s. 18H), 2.53 (s, 12H), 5.95 (d,2H, J=2.9 Hz), 6.64 (d, 2H, J=2.9 Hz), 6.68 (t, 2H, J=,7.5 Hz), 6.95 (t,2H, J=7.6 Hz 2H, J=8.5 Hz), 7.45 (d, 2H, J=8.8 Hz). 13C NMR (100 MHz,C₆D₆) δ 5.6, 47.9, 105.1, 111.5, 1122.2, 122.9, 124.2, 126.4, 128.5. ¹¹BNMR (115.5 MHz, C₆D₆) δ 50.3. HRMS (EI) calculated for C₂₈H₄₂BN₃Si₂Zr,577.2057;, found, 577.2061.

Example 20 Bis(trimethyl)silylamidobis(η-inden-1-yl)boranezirconiumdichloride

[1505] Bis(trimethylsilyl)amidoboron bis(inden-1-yl) (0.45 g, 1.12 mmol)and Zr(NMe₂)₄ (0.30 g, 1.12 mmol) were combined in THF to give anintermediate which was not further purified. Volatile components wereremoved under reduced pressure and replaced with CH₂Cl₂ (10 ml). Themixture was stirred with trimethylsilane chloride (1.42 ml, 11.20 mmol)overnight room temperature. Volatile components were again removed underreduced pressure and the residue was extracted with CH₂Cl₂ and filtered.The solution was concentrated, layered with pentane, and cooled to −78°C. to give the desired product (0.54 g, 86 percent) as an orange solid.

[1506]¹H NMR (500 MHz, C₆D₆): δ 0.20 (s, 18H), 5.54 (d, 2H, J=3.3 Hz),6.68 (dd, 2H, J=2.1, 0.9 Hz), 6.85 (t. 2H, J=7.0 Hz), 7.04 (dd, 2H,J=8.1, 1.1 Hz), 7.17 (m, 2H, overlapped with solvent residue peak), 7.33(d, 2H, J=8.4 Hz). ¹³C NMR (100 MHz, C₆D₆) δ 5.3, 112.8, 113.0, 123.6,126.5, 127.1, 127.8, 132.1. ¹¹B NMR (115.5 MHz, C₆D₆) δ 48.5. HRMS (EI)calculated for C₂₄H₃₀BNSi₂Cl₂Zr, 559.0434; found, 559.0432.

Example 21 Preparation of rac-diisopropylamidoborane-bis-η⁵-(2-isopropyl-4-phenyl indenyl)zirconium η⁴-1,4-diphenyl-1,3-butadiene

[1507]

[1508] 21A) 2-Isopropyl-4-phenyl indene

[1509] Sodium hydride (2.1 g , 60 percent dispersion in oil) was placedin 500 ml flask under nitrogen atmosphere. Hexane (about 20 ml) wasadded to remove the oil, the mixture was stirred briefly. After stirringstopped the NaH was allowed to settle and the the liquids were removedby syringe. This procedure was repeated once more, then THF (200 ml) wasadded to the NaH and the suspension was cooled with an ice bath. Diethylisopropylmalonate (10.10 g, 50.00 mmol) in THF (100 ml) was added via anaddition funnel over 30 min. After addition of the malonate wascomplete, the solution was stirred for an additional 40 min. A THFsolution (30 ml) of 2-phenylbenzyl bromide (12.5 g, 50.5 mmol) was addedvia addition funnel and the mixture was stirred overnight. The nextmorning 100 ml of 1N ammonium chloride was added. The solution wasdiluted with ether (200 ml) and the organic layer was washed with brine,dried over Na₂SO₄, and stripped of solvent under reduced pressure. Theorange red oil was used without further purification.

[1510] The crude alkylation product was dissolved in ethanol (300 ml)and water (75 ml). Potassium hydroxide (20 g) was added and the mixturewas refluxed overnight. After cooling, ethanol was stripped underreduced pressure. Hexane was added and stirred for 1 hour to dissolveany undesired organic materials. The hexane was decanted and water wasadded (about 150 ml). The solution was made acidic (to pH 1) by addingconcentrated HCl. The desired carboxylic product was extracted withether, dried over Na₂SO₄, and stripped under reduced pressure. NMRspectra of the crude product (10.74 g, 80 percent) indicated that esterhydrolysis and decarboxylation were complete. The crude product, whichsolidified to a tan solid, was used without further purification.

[1511] Thionyl chloride (50 ml) was added to the carboxylic acid and themixture was stirred overnight at room temperature to dissolve the acid.The excess thionyl chloride was removed under reduced pressure and theremaining acid chloride was dissolved in methylene chloride (75 ml).This solution was added dropwise via an addition funnel to a suspensionof aluminum chloride (5.70 g, 42.5 mmol) in methylene chloride (25 ml)and cooled with an ice bath. The reaction was allowed to warm slowly toroom temperature and stirred overnight. The solution was poured onto ice(about 100 ml) and stirred vigorously for 1 hour. The organic layer wasseparated, the aqueous layer was washed once with ether and the combinedorganic layers were washed with brine, dried over Na₂SO₄, and strippedunder reduced pressure. The crude 2-isopropyl-4-phenylindanone (10.0 g)as an orange-brown oil was used without further purification.

[1512] 2-isopropyl-4-phenylindanone (12.1 g, 48 mmol) was stirred in amixture of THF and methanol (100 ml, 2/1) while sodium borohydride (1.5g, 40 mmol) was added in small portions over 30 min. After stirringovernight, ice (about 50 ml) was added and the mixture was stirred for0.5 h. The THF and MeOH were removed under reduced pressure. Ether(about 250 ml) was added, the pH was adjusted to pH 1 by the addition ofaqueous HCl and the ether layer was separated. The ether was washed withsaturated sodium bicarbonate solution, then brine, dried over Na₂SO₄,and evaporated under reduced pressure. The mixture of alcohol isomers(11.0 g, 43.5 mmol, 90 percent) was obtained as a waxy tan solid. It wasused without purification.

[1513] The crude mix of isomeric alcohols was dissolved in toluene (150ml) to which p-toluene sulfonic acid (0.5 g) was added. The solution wasrefluxed in a flask equipped with a Dean-Stark trap for 1.5 h thencooled. Solid sodium bicarbonate was added and the mixture was storedovernight in a refrigerator. The next morning water (100 ml) was addedand the organic layer was separated, dried over Na₂SO₄, and strippedunder reduced pressure. The product, 2-isopropyl-4-phenylindene (10.4 g)was obtained as a brown oil. Analysis by GC indicated a purity of >96area percent. This material was stored cold under an inert atmosphereuntil ready for further conversion.

[1514]¹H-NMR (CDCl₃): δ 1.18 (d, 6H), 2.74 (sept, 1H), 3.39 (s, 2H),6.53 (s, 1H), 7.09-7.55 (m, 8H).

[1515] 21B) Lithium 2-isopropyl-4-phenylindenide

[1516] To a toluene solution (25 ml) of 2-isopropyl-4-phenylindene (3.34g, 14.25 mmol), in a glovebox filled with argon, was added n-butyllithium (5.500 ml, 13.75 mmol). The mixture was stirred at roomtemperature overnight. The toluene was removed under reduced pressure.Hexane (20 ml) was added and removed under reduced pressure then addedagain (50 ml). The mixture was stirred for 1 h then filtered, washedwith about 15 ml hexane and the filtrate dried under vacuum. The lithiumindenide product (3.09 g) was obtained as an orange-brown powder. Thismaterial was stored in the glovebox until needed.

[1517]¹H-NMR (d₈-THF): δ 1.27 (d, 6H), 3.02 (sept, 1H), 5.84 (s, 1H),6.06 (s, 1H), 6.42-6.51 (m, 2H), 7.15 (t, 1H), 7.18 (d, 1H), 7.26 (t,2H), 7.82 (d, 2H). ¹³C-NMR (d₈-THF): ppm 147.00, 141.54, 130.59, 130.40,129.20, 128.16, 126.70, 125.02, 118.68, 113.92, 113.40, 91.01, 89.77,30.62, 25.78.

[1518]21C) N,N-diisopropylamido bis(2-isopropyl-4-phenylindenyl) borane

[1519] To 25 ml toluene solution of N,N-diisopropylamidoboron dichloride(0.501 g, 2.75 mmole) at room temperature was added drop wise potassium(2-isopropyl-4-phenyl)indenide (1.50 g, 5.51 mmole in 20 ml toluene).The mixture was heated to reflux and stirred for 6 hours. The solutionwas cooled to room temperature, filtered through a medium frit, andsolvent was removed under reduced pressure to give a light yellow solid(1.57 g, 99 percent). This material was further purified by columnchromatography (silica gel/hexane) to yield 0.6 g (38 percent) of alight yellow solid (96 percent pure by GC).

[1520] 21D) rac-diisopropylamidoborane-bis-η⁵-(2-isopropyl-4-phenylindenyl)zirconium η⁴-1,4-diphenyl-1,3-butadiene

[1521] In a glove box, N,N-diisopropylaminobis(2-isopropyl-4-phenylindenyl) borane (0.380 g, 0.660 mmole) wasdissolved in 20 ml of toluene, 2.1 equivalents of potassiumbis(trimethylsilyl) amide (0.276, 1.38 mmole ) was added and theresulting mixture was stirred at room temperature for 24 hours. Removedvolatiles under reduced pressure and washed. The resulting orange solidwas combined with 10 ml of hexane, filtered and pumped dry. Thedipotassium salt residue (0.415 g, 97 percent, 0.635 mmole) wasredissolved in 20 ml of toluene, and(1,4-diphenyl-1,3-butadiene)bis(trimethylphosphine)zirconium dichloride(0.384 g, 0.635 mmole) was added. The solution was stirred for 2 h atroom temperature, followed by heating at 80° C. for 6 hours. The productmixture was cooled to room temperature, filtered through diatomaceousearth and the solvent of, the filtrate was removed under reducedpressure. Further purification was carried out by recrystallization fromhexane to yield 0.21 g (36 percent) of product as a dark red solid.

[1522]¹H NMR (C₆D₆): δ 7.62(d, 2H); 7.42−6.7, (mm, 24 H); 5.79 (s,2H);4.5, sept, 2H); 3.45-3.57 (dd, 2H); 2.8-2.9 (sept, ²H)1.65-1.72 (dd,2H); 1.35(d,12H); 1.2-1.3 (m, 12H).

Example 22 Supportedrac-diisopropylamidoborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconiumη⁴-1,4-diphenyl-1,3-butadiene

[1523] A toluene solution of methyldi(octyl)ammoniumhydroxyphenyltris-(pentafluorophenyl)borate (825 μl, 0.040M, 33.0 μmol,the ammonium cation being derived from a mixture of amines availablecommercially as methylbistallowamine) and a toluene solution of triethylaluminum (TEA) (363 μl, 0.10 M, 36.3 μmol) were combined and mixed for30 seconds. The resulting solution was then added to 1.0 g ofTEA-treated silica (Grace-Davison 948 silica, calcined at. 250° C. for 4h, treated with 1.5 mmol TEA/g, washed with toluene and mixed hexanesand dried under reduced pressure). The mixture was shaken by hand tobreak-up clumps and then mechanically agitated for 5 minutes. Thevolatile components were then removed under reduced pressure. A toluenesolution ofrac-diisopropylamidoborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconiumη⁴-1,4-diphenyl-1,3-butadiene (1500 μl, 0.020M, 30.0 μmol) was added.The mixture was shaken by hand to break-up clumps and then mechanicallyagitated for 5 minutes. The volatile components were once again removedunder reduce pressure to give the supported catalyst as a blue/graysolid.

Example 23 Supportedrac-dimethylamidoborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconiumη⁴-1,4-diphenyl-1,3-butadiene

[1524] A toluene solution of methyldi(octyl)ammoniumhydroxyphenyltris(penta-fluorophenyl)borate (578 μl, 0.040M, 23.1 μmol)and a toluene solution of trimethyl aluminum (254 μl, 0.100M, 25.4 μmol)were added and mixed for 30 seconds. This solution was then added to0.70 g of TEA-treated silica (Grace-Davison 948 silica, calcined at 250°C. for 4 h, treated with 1.5 mmol TEA/g, washed with toluene and hexanesand dried under reduced pressure). The mixture was shaken by hand tobreak-up clumps and then mechanically agitated for 5 minutes. Thevolatile components were then removed under reduced pressure. A toluenesolution of racdimethylamidoborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconiumη⁴-1,4-diphenyl-1,3-butadiene (1050 μl, 0.020M, 21.0 μmol) was added.The mixture was shaken by hand to break-up clumps and then mechanicallyagitated for 5 minutes. The volatile components were then removed underreduced pressure to give a teal blue solid.

Example 24 Supportedrac-diisopropylamidoborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconiumη⁴-1,4-diphenyl-1,3-butadiene

[1525] A toluene solution of methylbis(octadecyl)ammoniumbis(tris(penta-fluorophenyl)aluminane)imidazolide (689 μl, 0.0479M, 33.0μmol, prepared according to U.S. Ser. No. 09/251,664, filed Feb. 17,1999) was added to 1.0 g of TEA-treated (Grace-Davison 948 silica,calcined at 250° C. for 4 h, treated with 1.5 mmol TEA/g, washed withtoluene and hexanes and dried under reduced pressure). The mixture wasshaken by hand to break-up clumps and then mechanically agitated for 5minutes. The volatile components were then removed under reducedpressure. A toluene solution ofrac-diisopropylamidoborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconiumη⁴-1,4-diphenyl-1,3-butadiene (1500 μl, 0.020M, 30.0 μmol) was added.The mixture was shaken by hand to break-up clumps and then mechanicallyagitated for 5 minutes. The volatile components were then removed underreduced pressure to give a blue solid.

Example 25 Supportedrac-dimethylamidoborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconiumη⁴-1,4-diphenyl-1,3-butadiene

[1526] Under an argon atmosphere, a toluene solution ofmethylbis(octadecyl)ammoniumbis(tris(pentafluorophenyl)aluminane)imidazolide (689 μl, 0.0479M, 33.0μmol) was added to 1.0 g of TEA-treated (Grace-Davison 948 silica,cacined at 250° C. for 4 h, treated with 1.5mmol TEA/g, washed withtoluene and hexanes and dried under reduced pressure). The mixture wasshaken by hand to break-up clumps and then mechanically agitated for 5minutes. The volatile components were then removed under reducedpressure. A toluene solution ofrac-dimethylamidoborane-bis-η⁵-(2-methyl-4-phenylinden-1-yl)zirconiumη⁴-1,4-diphenyl-1,3-butadiene (1500 μl, 0.020M, 30.0 μmol) was added.The mixture was shaken by hand to break-up clumps and then mechanicallyagitated for 5 minutes. The volatile components were then removed underreduced pressure to give a light blue solid.

[1527] Gas Phase Polymerization

[1528] A 2.5-L stirred, fixed bed autoclave was charged with 200 g dryNaCl containing 0.1 g of KH as a scavenger. Stirring was begun at 300rpm. The reactor was pressurized to 0.8 MPa ethylene and heated to 72°C. 1-hexene was introduced to the reactor followed by the addition ofhydrogen. In a separate vessel, 0.05 g of catalyst was mixed with anadditional 0.1 g KH scavenger. The combined catalyst and scavenger weresubsequently injected into the reactor. Ethylene pressure was maintainedon demand while hexene and hydrogen were fed to the reactor to maintaintheir respective concentrations. The temperature of the reactor wasregulated by a circulating water bath. After 90 minutes the reactor wasdepressurized, and the salt and polymer were removed. The polymer waswashed with copious quantities of distilled water to remove the salt,dried at 60° C., and then stabilized by addition of a hindered phenolantioxidant (Irganox™ 1010 from Ciba Geigy Corporation) and 133 mg of aphosphorus stabilizer. Activity values were calculated based on ethyleneuptake. Results are contained in Table 1. TABLE 1 hexene H₂ MMI³ Mw ×Run Cat. (ppm) (ppm) Activity¹ Density² (dg/m) 10⁻³ MWD I₁₀/I₂ 1 Ex. 225000 0 122.7 0.899 <0.01 315 2.84 — 2 Ex. 23 5000 0 115.0 0.900 <0.01301 2.92 — 3 ″ 4000 500 84.1 0.905 <0.01 272 3.07 — 4 ″ 5000 0 134.10.899 <0.01 323 2.26 — 5 ″ 5000 3000 120.0 0.898 <0.01 222 3.24 — 6 ″5000 6000 116.7 0.900 <0.01 192 2.50 — 7 Ex. 24 5000 6000 140.7 0.8990.026 180 3.16 34.2 8 Ex. 25 5000 6000 54.0 0.898 <0.01 194 2.56 9⁴ Ex.23 5000 8000 133.8 0.901 0.04 187 2.84 23.0

16. (New) an olefin polymerization process comprising contacting one ormore olefin monomers under gas phase polymerization conditions with acatalyst composition comprising a metal complex corresponding to thefollowing formula:

wherein: M is titanium, zirconium, or hafnium in the +4, +3, or +2oxidation state; Y¹ and Y² are independently an anionic, cyclic ornon-cyclic, π-bonded group, NR¹, PR¹; NR¹ ₂ or PR¹ ₂; Z is boron oraluminum; Q is a neutral, anionic or dianionic ligand group depending onthe oxidation state of M; j is 1, 2 or 3 depending on the oxidationstate of M and the electronic nature of Q; T independently eachoccurrence is:

wherein R¹ is independently each occurrence hydrogen, a hydrocarbylgroup, a tri(hydrocarbyl)silyl group, or atri(hydrocarbyl)silylhydrocarbyl group, said R¹ groups containing up to20 atoms not counting hydrogen; R⁵ is R¹ or N(R¹)₂; and two R¹ groupstogether or one or more R¹ groups together with R⁵ may optionally bejoined to form a ring structure.
 17. (New) The process of claim 16wherein the metal complex corresponds to the following formulas:

wherein R² is hydrogen, or a hydrocarbyl, halohydrocarbyl,dihydrocarbylaminohydrocarbyl, tri(hydrocarbylsilyl)hydrocarbyl,Si(R³)₃, N(R³)₂, or OR³ group of up to 20 carbon or silicon atoms, andoptionally two adjacent R² groups can be joined together, therebyforming a fused ring structure, especially an indenyl ligand or asubstituted indenyl ligand; and R³ is independently hydrogen, ahydrocarbyl group, a trihydrocarbylsilyl group or atrihydrocarbylsilylhydrocarbyl group, said R³ having up to 20 atoms notcounting hydrogen.
 18. (New) The process of claim 17 wherein M is in the+4 oxidation state, j=2 and Q independently each occurrence is halide,hydride, hydrocarbyl, silylhydrocarbyl, hydrocarbyloxide, ordihydrocarbylamide, said Q having up to 20 atoms not counting hydrogen,or two Q groups together form an alkanediyl group or a conjugated C₄₋₄₀diene ligand that together with M form a metallocyclopentene.
 19. (New)The process of claim 17 wherein M is in the +3 oxidation state, j=1 andQ is either 1) a monovalent anionic stabilizing ligand selected from thegroup consisting of alkyl, cycloalkyl, aryl, silyl, amido, phosphido,alkoxy, aryloxy, sulfido groups, and mixtures thereof, said Q beingfurther substituted with an amine, phosphine, ether, or thioethercontaining substituent able to form a coordinate-covalent bond orchelating bond with M said ligand having up to 50 atoms not countinghydrogen; or 2) a C₃₋₁₀ hydrocarbyl group comprising an ethylenicunsaturation able to form an η³-bond with M.
 20. (New) The process ofclaim 17 wherein M is in the +2 oxidation state, j=1 and Q is a neutralconjugated diene, optionally substituted with one or moretri(hydrocarbyl)silyl or tri(hydrocarbylsilyl)hydrocarbyl groups, said Qhaving up to 40 carbon atoms and forming a π-complex with M.
 21. (New)The process of claim 18 wherein the metal complex corresponds to thefollowing formulas:

wherein Q independently each occurrence is a halide, hydrocarbyl,hydrocarbyloxy, or dihydrocarbylamide group of up to 10 atoms notcounting hydrogen, or two Q groups together form a C₄₋₂₀ diene ligandthat together with M forms a metallocyclopentene.
 22. (New) The processof claim 19 wherein the metal complex corresponds to the followingformulas:

wherein Q each occurrence is a monovalent anionic stabilizing ligandselected from the group consisting of alkyl, cycloalkyl, aryl, and silylgroups, said group being further substituted with one or more amine,phosphine, or ether substituents able to form a coordinate-covalent bondor chelating bond with M, and said Q having up to 30 non-hydrogen atoms;or Q is a C₃₋₁₀ hydrocarbyl group comprising an ethylenic unsaturationable to form an η³ bond with M.
 23. (New) The process of claim 20wherein the metal complex corresponds to the following formulas:

wherein Q each occurrence is a neutral conjugated diene, optionallysubstituted with one or more tri(hydrocarbyl)silyl groups ortri(hydrocarbyl)silylhydrocarbyl groups, said Q having up to 30 atomsnot counting hydrogen and forming a π-complex with M.
 24. (New) Theprocess of any one of claims 16-23 wherein M is zirconium or hafnium.25. (New) The process of claim 24 wherein Z is boron.
 26. (New) Theprocess of claim 16 wherein the metal complex isdichloro-[1,2-Bis(2,6-diisopropylanilide)-1,2-bis(dimethylamido)diborane]titanium,dimethyl[1,2-Bis(2,6-diisopropylanilide)-1,2-bis(dimethylamido)diborane]titanium,dibenzyl[1,2-Bis(2,6-diisopropylanilide)-1,2-bis(dimethylamido)diborane]zirconium,orrac-1,2-bis(dimethylamidodiborane)bis(2-methyl-4-phenylinden-1-yl)zirconiumη⁴-diphenyl-1,3-butadiene.
 27. (New) The process of claim 16 wherein thecatalyst additionally comprises a support material.
 28. (New) Theprocess of claim 16 which is a continuous gas phase polymerization. 29.(New) The process of claim 28 wherein ethylene is homopolymerized, or amixture of C₂₋₆ olefins is copolymerized.
 30. (New) The process of anyone of claims 16, 28 or 29 wherein the resulting polymer contains longchain branching.